Cyclic azine derivatives, processes for producing these, and organic electroluminescent element containing these as component

ABSTRACT

A cyclic azine compound represented by general formula (1): 
                         
wherein each Ar 1  represents an aromatic group, which is unsubstituted or substituted by a C 1-4  alkyl group, a phenyl group or a pyridyl group; and A represents a group selected from those which are represented by general formulae (2) to (5), described in the description. The cyclic azine compound is useful for an organic compound layer of fluorescent or phosphorescent EL device.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional application of U.S. applicationSer. No. 13/391,046, which is a National Stage of International PatentApplication No. PCT/JP2010/064070, filed Aug. 20, 2010. The entiredisclosures of these applications are expressly incorporated byreference herein.

TECHNICAL FIELD

This invention relates to cyclic azine compounds having two differentsubstituents on an azine ring, and a process for producing the cyclicazine compounds.

The cyclic azine compounds exhibit good charge-transporting property,therefore, are useful as a component of a fluorescent or phosphorescentorganic electroluminescent device.

Thus, this invention further relates to an organic electroluminescentdevice having at least one organic compound layer containing the cyclicazine derivative as a component, which is a highly efficient organicelectroluminescent device exhibiting improved drivability and lightemission.

BACKGROUND ART

An organic electroluminescent (hereinafter abbreviated to “EL” whenappropriate) device has a multilayer structure comprising (i) aluminescent layer comprising a light emitting material and (ii) a holetransport layer and an electron transport layer, which sandwich theluminescent layer, and (iii) an anode and a cathode, which sandwich thehole transport layer, the luminescent layer and the electron transportlayer. The organic EL device utilizes light emission (fluorescence orphosphorescence) occurring at deactivation of an exciton formed by therecombination of electron with hole, which are injected in theluminescent layer. The organic EL device is widely used for a displayand other applications.

Patent documents 1 and 2 disclose organic EL device containing apyrimidine compound as a luminescent material. The pyrimidine compoundincludes those which have a substituted phenyl substituent at a2-position in the pyrimidine ring, but, the positions at whichsubstituents are bonded to the phenyl substituent are not limited. Thesepatent documents are silent on pyrimidine compounds having a substitutedphenyl substituent at a 2-position in the pyrimidine ring, which has twospecific substituents at 3- and 5-positions of the phenyl substituent.Thus, these patent documents are silent on a pyrimidine compounds of theformula (1a), described below, of the present invention which has asubstituted phenyl substituent at a 2-position in the pyrimidine ring,which has two specific substituents at 3- and 5-positions of the phenylsubstituent.

Patent documents 3 and 4 disclose an organic EL device containing apyrimidine compound having a 4-substituted phenyl substituent. However,these documents are silent on a pyrimidine compound of the formula (1a),described below, of the present invention which has a substituted phenylsubstituent at a 2-position in the pyrimidine ring, which has twospecific substituents at 3- and 5-positions of the phenyl substituent.

Patent document 5 discloses an organic EL device containing a pyrimidinecompound having a phenyl group condensed with an aromatic hetero5-membered ring. However, this document is silent on a pyrimidinecompound of the formula (1a), described below, of the present inventionwhich has a substituted phenyl substituent at a 2-position in thepyrimidine ring, which has two substituents at 3- and 5-positions of thephenyl substituent.

Patent document 6 discloses an organic EL device containing a pyrimidinecompound. As one example of the pyrimidine compounds, a pyrimidinecompound having a substituted phenyl substituent at 2-position of thepyrimidine ring, wherein the phenyl substituent has two phenyl groups at3- and 5-positions of the phenyl substituent. The two phenyl groups at3- and 5-positions thereof have no substituent. In contrast, thepyrimidine compounds of the formula (1a), described below, of thepresent invention has a substituted phenyl substituent at a 2-positionin the pyrimidine ring, which has two specific substituents at 3- and5-positions of the phenyl substituent, wherein each substituent is aphenyl group having a substituent or a condensed aromatic hydrocarbongroup. Thus, the pyrimidine compound disclosed in patent document 6 isdistinguished from the pyrimidine compound of the formula (1a). Thepyrimidine compound disclosed in patent document 6 is also distinguishedfrom the pyrimidine compound of the formula (1c), described below, ofthe present invention.

Patent document 7 discloses an organic EL device containing a pyrimidinecompound. This pyrimidine compound has no polycyclic aromatic group, andthus, is distinguished from the pyrimidine compounds of the formulae(1b) and (1c) of the present invention.

Patent documents 8 and 9 disclose an organic EL device containing1,3,5-triazine compounds having polycyclic aromatic groups. The triazinecompounds are characterized as exhibiting a structural isomerismoccurring steric hindrance, and thus, these compounds are distinguishedfrom the pyrimidine compounds of the formulae (1b) and (1c) of thepresent invention. In patent document 8, there is no working examplewherein a 1,3,5-triazine compound having a phenyl group bonded to thetriazine ring, said phenyl group having two aromatic hydrocarbon groupseach having 2 to 4 rings. Further the two patent documents 8 and 9suggest nothing about the glass transition temperature (Tg) and electronmobility of the triazine compound.

More specifically patent documents 8 and 9 give only working exampleswherein 1,3,5-triazie compounds having the same substituents at 2-, 4-and 6-positions thereof are described, and any description of glasstransition temperature (Tg) is not specifically given.

For the use as a basic material of an organic EL device, a thin film ofthe basic material must be amorphous and have smooth surface. A triazinecompound having a highly symmetrical skeletal is highly crystalline,therefore, unsatisfactory for the basic material of the EL device. Thecyclic azine compound of the formula (1d), described below, of thepresent invention has a structure such that different substituents arearranged at 2-, 4- and 6-positions of a 1,3,5-triazine ring, and thuscrystallization of a thin film of the cyclic azine compound iscontrolled. The cyclic azine compound of the present invention hascharacteristics occurring due to the molecule skeletal which aredistinguished from those of the triazine compound having a symmetricalskeletal.

Patent document 10 discloses a nitrogen-containing heterocyclic compoundfor use in an organic EL device. As one example of the heterocycliccompound, a compound having a 1,3,5-triazine ring and a pyrenyl group ismentioned (Table 12, No. 6-13). However, any specific explanation ofthis compound and working example thereof are not given, and Tg andelectron mobility thereof are not mentioned.

Patent documents 9 and 11 disclose a cyclic azine compound, i.e.,1,3,5-triazine compound for use in an organic EL device. This triazinecompound includes those which have substituted phenyl groups at 2-, 4-and 6-positions of the triazine ring, but, the positions of thesubstituents of the phenyl groups are not limited. These patentdocuments are silent on the cyclic azine compound of the formula (1c) ofthe present invention, said azine compound having a phenyl group at2-position of the triazine ring, which phenyl group has3,5-di-substituted phenyl groups or 2,6-di-substituted pyridyl groups.

PRIOR ART DOCUMENTS Patent Documents

Patent document 1: JP 2003-45662

Patent document 2: JP 2004-31004

Patent document 3: WO 2004/039786

Patent document 4: WO 2005/105950

Patent document 5: WO 2007/069569

Patent document 6: WO 2005/085387

Patent document 7: JP 2008-280330

Patent document 8: JP 2001-143869

Patent document 9: JP 2004-22334

Patent document 10: JP 2004-2297

Patent document 11: JP 2007-137829

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

An object of the present invention is to provide a cyclic azine compoundhaving a novel chemical structure which gives, when it is used as abasic material for an organic EL device, an organic EL device exhibitingimproved drivability at a low voltage and enhanced light emission with ahigh efficiency; an organic EL device having high glass transitiontemperature and high electron mobility; or an organic EL elementexhibiting good charge-injection and charge-transport property andhaving enhanced durability and life.

Another object of the present invention is to provide an industriallyadvantageous process for producing the above-mentioned cyclic azinecompound.

A further object of the present invention is to provide an industriallyadvantageous organic EL device containing the above-mentioned cyclicazine compound as a constitutional component.

Means for Solving the Problems

The inventors made an extensive search to solve the above-mentionedproblems, and have found that a cyclic azine compound of the formula (1)having two different substituents on the azine ring according to thepresent invention can be formed into a thin film by the conventionalprocedure such as vacuum deposition and spin coating, and the thin filmexhibits good electron transport characteristics. The inventors furtherhave found that a fluorescent or phosphorescent organic EL device havingan organic compound layer comprised of the cyclic azine compound ischaracterized as confining an exciton therein with high efficiency, andhence, as exhibiting enhanced drivability at a low voltage as well asimproved light emission with high efficiency.

Thus, in one aspect of the present invention, there is provided a cyclicazine compound represented by the general formula (1):

wherein, in the formula (1), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; and

A represents a group selected from the group consisting of those whichare represented by the following general formulae (2) to (5).

wherein, in the formula (2), each Ar² represents a substituted phenylgroup or a condensed aromatic hydrocarbon group not having a 16 groupelement, provided that a 1,3,5-trimethylphenyl group is excluded fromAr²;

wherein, in the formula (3), Ar³ represents a phenyl group, a pyridylgroup or a pyrimidyl group; Ar⁴ represents a substituted orunsubstituted aromatic hydrocarbon group having 2 to 4 rings; Xrepresents a phenylene group or a pyridylene group; p represents aninteger of 0 to 2 provided that, when p is 2, the two Xs may be the sameor different; and Z¹ represents a carbon or nitrogen atom;

wherein, in the formula (4), each Ar⁵ and each Ar⁶ represent a phenylgroup or a pyridyl group; Z² and each Z³ represent a carbon atom or anitrogen atom, provided that, when each Z³ represents a carbon atom,each Ar⁵ and each Ar⁶ cannot represent simultaneously a phenyl group;and

wherein, in the formula (5), each Ar⁴ independently represents anaromatic hydrocarbon group having 2 to 4 rings.

In another aspect of the present invention, there is provided a processfor preparing a cyclic azine compound represented by the general formula(1a):

wherein, in the formula (1a), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; and each Ar² representsa substituted phenyl group or a condensed aromatic hydrocarbon group nothaving a 16 group element, provided that a 1,3,5-trimethylphenyl groupis excluded from Ar²;

characterized by coupling a compound represented by the general formula(6) with a compound represented by the general formula (7) in thepresence of a palladium catalyst and in the presence or absence of abase;

wherein, in the formula (6), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; and each Y¹ representsa chlorine, bromine or iodine atom;Ar²-M  (7)

wherein, in the formula (7), Ar² represents a substituted phenyl groupor a condensed aromatic hydrocarbon group not having a 16 group element,provided that a 1,3,5-trimethylphenyl group is excluded from Ar²; and Mrepresents a metal group or a hetero atom group.

In still another aspect of the present invention, there is provided aprocess for preparing a cyclic azine compound represented by the generalformula (1a):

wherein, in the formula (1a), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; and each Ar² representsa substituted phenyl group or a condensed aromatic hydrocarbon group nothaving a 16 group element, provided that a 1,3,5-trimethylphenyl groupis excluded from Ar²;

characterized by coupling a compound represented by the general formula(8) with a compound represented by the general formula (9) in thepresence of a palladium catalyst and a base;

wherein, in the formula (8), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; each R¹ represents ahydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenylgroup; and groups R¹ in the two —B(OR¹) groups may be the same ordifferent, and two groups R¹ in each of the two —B(OR¹) groups may forma ring together with the oxygen atoms and the boron atom;Ar²—Y¹  (9)

wherein, in the formula (9), Ar² represents a substituted phenyl groupor a condensed aromatic hydrocarbon group not having a 16 group element,provided that a 1,3,5-trimethylphenyl group is excluded from Ar²; and Y¹represents a chlorine, bromine or iodine atom.

In a further aspect of the present invention, there is provided aprocess for preparing a cyclic azine derivative represented by thegeneral formula (1b):

wherein, in the formula (1b), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; Ar³ represents a phenylgroup, a pyridyl group or a pyrimidyl group; Ar⁴ represents asubstituted or unsubstituted aromatic hydrocarbon group having 2 to 4rings; X represents a phenylene group or a pyridylene group; prepresents an integer of 0 to 2 provided that, when p is 2, the two Xsmay be the same or different; and Z represents a carbon or nitrogenatom;

characterized by coupling a compound represented by the general formula(10) with a compound represented by the general formula (11) in thepresence of a palladium catalyst and in the presence or absence of abase;

wherein, in the formula (10), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; Ar⁴ represents asubstituted or unsubstituted aromatic hydrocarbon group having 2 to 4rings; Z¹ represents a carbon or nitrogen atom; and Y¹ represents achlorine, bromine or iodine atom;Ar³—Xp-M  (11)

wherein, in the formula (11), Ar³ represents a phenyl group, a pyridylgroup or a pyrimidyl group; X represents a phenylene group or apyridylene group; p represents an integer of 0 to 2 provided that, whenp is 2, the two Xs may be the same or different; and M represents ametal group or a hetero atom group.

In a further aspect of the present invention, there is provided aprocess for preparing a cyclic azine compound represented by the generalformula (1c):

wherein, in the formula (1c), each Ar¹ represents an aromatic groupwhich is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; each Ar⁵ and each Ar⁶represent a phenyl group or a pyridyl group; and Z² and each Z³represent a carbon or nitrogen atom, provided that, when each Z³represents a carbon atom, each Ar⁵ and each Ar⁶ cannot be simultaneouslya phenyl group;

characterized by coupling a compound represented by the general formula(12) with a compound represented by the general formula (13) in thepresence of a palladium catalyst and a base;

wherein, in the formula (12), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; Z² represents a carbonor nitrogen atom; each R¹ represents a hydrogen atom, an alkyl grouphaving 1 to 4 carbon atoms or a phenyl group; and groups R¹ in the two—B(OR¹)₂ groups may be the same or different, and two groups R¹ in eachof the two —B(OR¹)₂ groups may form a ring together with the oxygenatoms and the boron atom;

wherein, in the formula (13), Ar⁵ and Ar⁶ represent a phenyl group or apyridyl group; and Z³ represents a carbon or nitrogen atom, providedthat, when Z³ represents a carbon atom, Ar⁵ and Ar⁶ cannot besimultaneously a phenyl group; and Y¹ represents a chlorine, bromine oriodine atom.

In a further aspect of the present invention, there is provided aprocess for preparing a cyclic azine compound represented by the generalformula (1d):

wherein, in the formula (1d), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; and each Ar⁴independently represents an unsubstituted or substituted aromatichydrocarbon group having 2 to 4 rings;

characterized by coupling a compound represented by the general formula(14) with a compound represented by the general formula (15) in thepresence of a palladium catalyst and a base;

wherein, in the formula (14), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; each R¹ represents ahydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenylgroup; and groups R¹ in the two —B(OR¹)₂ groups may be the same ordifferent, and two groups R¹ in each of the two —B(OR¹)₂ groups may forma ring together with the oxygen atoms and the boron atom;Ar⁴—Y¹  (15)

wherein, in the formula (15), Ar⁴ represents an unsubstituted orsubstituted aromatic hydrocarbon group having 2 to 4 rings; and Y¹represents a chlorine, bromine or iodine atom.

In a further aspect of the present invention, there is provided anorganic electroluminescent device comprising as a constituent a cyclicazine compound represented by the general formula (1):

wherein, in the formula (1), each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; and

A represents a group selected from the group consisting of those whichare represented by the following general formulae (2) to (5):

wherein, in the formula (2), each Ar² represents a substituted phenylgroup or a condensed aromatic hydrocarbon group not having a 16 groupelement, provided that a 1,3,5-trimethylphenyl group is excluded fromAr²;

wherein, in the formula (3), Ar³ represents a phenyl group, a pyridylgroup or a pyrimidyl group; Ar⁴ represents a substituted orunsubstituted aromatic hydrocarbon group having 2 to 4 rings; Xrepresents a phenylene group or a pyridylene group; p represents aninteger of 0 to 2 provided that, when p is 2, the two Xs may be the sameor different; and Z¹ represents a carbon or nitrogen atom;

wherein, in the formula (4), each Ar⁵ and each Ar⁶ represent a phenylgroup or a pyridyl group; Z² and each Z³ represent a carbon atom or anitrogen atom, provided that, when each Z³ represents a carbon atom,each Ar⁵ and each Ar⁶ cannot represent simultaneously a phenyl group;and

wherein, in the formula (5), each Ar⁴ independently represents anaromatic hydrocarbon group having 2 to 4 carbon atoms.

Effect of the Invention

The cyclic azine derivative having a novel chemical structure accordingto the present invention gives, when it is used as a basic material fora fluorescent or phosphorescent organic EL device, an organic EL deviceexhibiting improved drivability at a low voltage and enhanced lightemission with a high efficiency.

More specifically, a thin film comprised of the cyclic azine compound ofthe present invention has high surface smoothness, amorphousness, heatresistance, electron transportability, hole block capability, resistanceto oxidation and reduction, moisture resistance, oxygen resistance andelectron injection characteristics, and therefore, the thin film issuitable as a component an organic EL device, especially useful aselectron transport material, hole blocking material and fluorescent hostmaterial.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a schematic cross-section of an example of an organicEL device having a thin film layer comprised of the cyclic azinecompound of the present invention.

EXPLANATION OF REFERENCE NUMERALS

1. Glass substrate with transparent ITO electrode

2. Hole injection layer

3. Hole transport layer

4. Light emitting layer

5. Electron transport layer

6. Cathode layer

MODE FOR CARRYING OUT THE INVENTION

The invention will now be described in detail.

In the general formula (1), each Ar¹ represents an aromatic group, whichis unsubstituted or substituted by an alkyl group having 1 to 4 carbonatoms, a phenyl group or a pyridyl group. Ar¹ includes, for example, aphenyl group which is unsubstituted or substituted by an alkyl grouphaving 1 to 4 carbon atoms, a phenyl group or a pyridyl group; anaphthyl group which is unsubstituted or substituted by an alkyl grouphaving 1 to 4 carbon atoms, a phenyl group or a pyridyl group; ananthryl group which is unsubstituted or substituted by an alkyl grouphaving 1 to 4 carbon atoms, a phenyl group or a pyridyl group; aphenanthryl group which is unsubstituted or substituted by an alkylgroup having 1 to 4 carbon atoms, a phenyl group or a pyridyl group; anda pyridyl group which is unsubstituted or substituted by an alkyl grouphaving 1 to 4 carbon atoms, a phenyl group or a pyridyl group.

Specific examples of such unsubstituted or substituted aromatic groupsare mentioned below, but should not be limited thereto.

As specific examples of the phenyl group which is unsubstituted orsubstituted by an alkyl group having 1 to 4 carbon atoms, a phenyl groupor a pyridyl group, there can be mentioned phenyl group, and substitutedphenyl groups such as a p-tolyl group, m-tolyl group, o-tolyl group,4-trifluoramethylphenyl group, 3-trifluromethylphenyl group,2-trifluromethylphenyl group, 2,4-dimethylphenyl group,3,5-dimethylphenyl group, 2,6-dimethylphenyl group, a mesityl group,2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group,2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group,3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group,3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenylgroup, 4-isopropylphenyl group, 2,4-diisopropylphenyl group,3,5-diisopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group,4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group,2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenylgroup, 2,4-di-tert-butylphenyl group and 3,5-di-tert-butylphenyl group;biphenyl groups such as 4-biphenylyl group, 3-biphenylyl group and2-biphenylyl group; terphenyl groups such as 1,1′:4′,1″-terphenyl-3-ylgroup, 1,1′:4′,1″-terphenyl-4-yl group, 1,1′:3′,1″-terphenyl-3-yl group,1,1′:3′,1″-terphenyl-4-yl group, 1,1′:3′,1″-terphenyl-5′-yl group,1,1′:2′,1″-terphenyl-3-yl group, 1,1′:2′,1″-terphenyl-4-yl group and1,1′:2′,1″-terphenyl-4′-yl group; and 2-(2-pyridyl)phenyl group,3-(2-pyridyl)phenyl group, 4-(2-pyridyl)phenyl group,2-(3-pyridyl)phenyl group, 3-(3-pyridyl)phenyl group,4-(3-pyridyl)phenyl group, 2-(4-pyridyl)phenyl group,3-(4-pyridyl)phenyl group and 4-(4-pyridyl)phenyl group.

Of these, as the unsubstituted or substituted phenyl groups, phenylgroup, p-tolyl group, m-tolyl group, o-tolyl group, 2,6-dimethylphenylgroup, 4-tert-butylphenyl group, 4-biphenylyl group, 3-biphenylyl group,2-biphenylyl group; 1,1′:4′,1″-terphenyl-4-yl group,1,1′:2′,1″-terphenyl-4-yl group, 1,1′:3′,1″-terphenyl-5′-yl group,3-(2-pyridyl)phenyl group, 4-(2-pyridyl)phenyl group,3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group,3-(4-pyridyl)phenyl group and 4-(4-pyridyl)phenyl group are preferablein view of the performance thereof as a material for an organicelectroluminescent device. Phenyl group, p-tolyl group, 4-biphenylylgroup, 2-biphenylyl group and 4-(3-pyridyl)phenyl are especiallypreferable in view of ease in synthesis.

As specific examples of the unsubstituted or substituted naphthylgroups, there can be mentioned 1-naphthyl group and 2-naphthyl group;and 4-methylnaphthalen-1-yl group, 4-trifluoromethylnaphthalen-1-ylgroup, 4-ethylnaphthalen-1-yl group, 4-propylnaphthalen-1-yl group,4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group,5-methylnaphthalen-1-yl group, 5-trifluoromethylnaphthalen-1-yl group,5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group,5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group,6-methylnaphthalen-2-yl group, 6-trifluoroamethylnaphthalen-2-yl group,6-ethylnaphthalen-2-yl group, 6-propylnaphthalen-2-yl group,6-butylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group,7-methylnaphthalen-2-yl group, 7-trifluoromethylnaphthalen-2-yl group,7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group,7-butylnaphthalen-2-yl group and 7-tert-butylnaphthalen-2-yl group.

Of these, as the unsubstituted or substituted naphthyl groups,1-naphthyl group, 4-methylnaphthalene-1-yl group,4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group,5-tert-butylnaphthalen-1-yl group, 2-naphthyl group,6-methylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group,7-methylaphthalene-2-yl group and 7-tert-butylnaphthalen-2-yl group arepreferable in view of the performance thereof as a material for anorganic electroluminescent device. 2-Naphthyl group is especiallypreferable because of ease in synthesis.

As specific examples of the unsubstituted or substituted anthryl groups,there can be mentioned 1-anthryl group, 2-anthryl group and 9-anthrylgroup; and 2-methylanthracen-1-yl group, 3-methylanthracen-1-yl group,4-methylanthracen-1-yl group, 9-methylanthracen-1-yl group,10-methylanthracen-1-yl group, 2-phenylanthracen-1-yl group,3-phenylanthracen-1-yl group, 4-phenylanthracen-1-yl group,5-phenylanthracen-1-yl group, 6-phenylanthracen-1-yl group,7-phenylanthracen-1-yl group, 8-phenylanthracen-1-yl group,9-phenylanthracen-1-yl group, 10-phenylanthracen-1-yl group,1-methylanthracen-2-yl group, 3-methylanthracen-2-yl group,4-methylanthracen-2-yl group, 9-methylanthracen-2-yl group,10-methylanthracen-2-yl group, 1-phenylanthracen-2-yl group,3-phenylanthracen-2-yl group, 4-phenylanthracen-2-yl group,5-phenylanthracen-2-yl group, 6-phenylanthracen-2-yl group,7-phenylanthracen-2-yl group, 8-phenylanthracen-2-yl group,9-phenylanthracen-2-yl group, 10-phenylanthracen-2-yl group,2-methylanthracen-9-yl group, 3-methylanthracen-9-yl group,4-methylanthracen-9-yl group, 10-methylanthracen-9-yl group,2-phenylanthracen-9-yl group, 3-phenylanthracen-9-yl group,4-phenylanthracen-9-yl group, 5-phenylanthracen-9-yl group,6-phenylanthracen-9-yl group, 7-phenylanthracen-9-yl group,1-phenylanthracen-9-yl group and 10-phenylanthracen-9-yl group.

Of these, as the unsubstituted or substituted anthryl groups, 1-anthrylgroup, 2-anthryl group, 9-anthryl group, 4-phenylanthracen-1-yl groupand 4-phenylanthracen-9-yl group are preferable in view of theperformance thereof as a material for an organic electroluminescentdevice. 1-Anthryl group, 2-anthryl group and 9-anthryl group areespecially preferable because of low molecular weight.

As specific examples of the unsubstituted or substituted phenanthrylgroups, there can be mentioned 1-phenanthryl group, 2-phenanthryl group,3-phenanthryl group, 4-phenanthryl group and 9-phenanthryl group; and2-phenylphenanthren-1-yl group, 3-phenylphenanthren-1-yl group,4-phenylphenanthren-1-yl group, 9-phenylphenanthren-1-yl group,1-phenylphenanthren-2-yl group, 3-phenylphenanthren-2-yl group,4-phenylphenanthren-2-yl group, 8-phenylphenanthren-2-yl group,8-phenylphenanthren-3-yl group, 9-phenylphenanthren-2-yl group,1-phenylphenanthren-3-yl group, 2-phenylphenanthren-3-yl group,4-phenylphenanthren-3-yl group, 9-phenylphenanthren-3-yl group,1-phenylphenanthren-4-yl group, 2-phenylphenanthren-4-yl group,3-phenylphenanthren-4-yl group, 9-phenylphenanthren-4-yl group,1-phenylphenanthren-9-yl group, 2-phenylphenanthren-9-yl group,3-phenylphenanthren-9-yl group and 4-phenylphenanthren-9-yl group.

Of these, as the unsubstituted or substituted phenanthryl groups,2-phenanthryl group, 3-phenanthryl group, 8-phenylphenanthren-2-yl groupand 8-phenylphenanthren-3-yl group are preferable in view of theperformance thereof as a material for an organic electroluminescentdevice. 2-Phenanthryl group and 3-phenanthryl group are especiallypreferable because of low molecular weight.

As specific examples of the unsubstituted or substituted pyridyl groups,there can be mentioned 2-pyridyl group, 3-pyridyl group and 4-pyridylgroup; and 3-methylpyridin-2-yl group, 4-methylpyridin-2-yl group,5-methylpyridin-2-yl group, 6-methylpyridin-2-yl group,2-methylpyridin-3-yl group, 4-methylpyridin-3-yl group,5-methylpyridin-3-yl group, 6-methylpyridin-3-yl group,2-methylpyridin-4-yl group, 3-methylpyridin-4-yl group,3-ethylpyridin-2-yl group, 4-ethylpyridin-2-yl group,2-ethylpyridin-3-yl group, 5-ethylpyridin-3-yl group,2-ethylpyridin-4-yl group, 3-ethylpyridin-4-yl group,3-propylpyridin-2-yl group, 4-butylpyridin-2-yl group,5-butylpyridin-2-yl group, 2-propylpyridin-3-yl group,2-butylpyridin-4-yl group, 4-tert-butylpyridin-2-yl group,5-tert-butylpyridin-2-yl group, 6-tert-butylpyridin-2-yl group,5-tert-butylpyridin-3-yl group, 6-tert-butylpyridin-3-yl group,2-tert-butylpyridin-4-yl group, 3-phenylpyridin-2-yl group,4-phenylpyridin-2-yl group, 5-phenylpyridin-2-yl group,6-phenylpyridin-2-yl group, 2-phenylpyridin-3-yl group,4-phenylpyridin-3-yl group, 5-phenylpyridin-3-yl group,6-phenylpyridin-3-yl group, 2-phenylpyridin-4-yl group and3-phenylpyridin-4-yl group.

Of these, as the unsubstituted or substituted pyridyl groups, 2-pyridylgroup, 3-pyridyl group, 4-pyridyl group, 4-methylpyridin-2-yl group,6-methylpyridin-2-yl group, 6-methylpyridin-3-yl group,4-tert-butylpyridin-2-yl group and 6-tert-butylpyridin-2-yl group arepreferable in view of the performance thereof as a material for anorganic electroluminescent device. 2-Pyridyl group is especiallypreferable because of ease in synthesis.

In the general formula (2), a substituted phenyl group represented byeach Ar² includes, for example, a phenyl group substituted by an alkylgroup having 1 to 4 carbon atoms, provided that 1,3,5-trimethylphenylgroup is excluded from the alkyl-substituted phenyl group; a phenylgroup substituted by a halogen atom; a phenyl group substituted by anunsubstituted or substituted phenyl group; a phenyl group substituted byan unsubstituted or substituted pyrimidinyl group; a phenyl groupsubstituted by an unsubstituted or substituted thiazolyl group; a phenylgroup substituted by a pyridyl group; and a phenyl group substituted bya phenanthrolinyl group.

Specific examples of the substituted phenyl group are mentioned below,but should not be limited thereto.

As specific examples of the phenyl group substituted by an alkyl grouphaving 1 to 4 carbon atoms, there can be mentioned p-tolyl group,m-tolyl group, o-tolyl group, 4-trifluoromethylphenyl group,3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group,2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenylgroup, a mesityl group, 2-ethylphenyl group, 3-ethylphenyl group,4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group,2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group,2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-isopropylphenylgroup, 3-isopropylphenyl group, 4-isopropylphenyl group,2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2-butylphenylgroup, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenylgroup, 3,5-dibutylphenyl group, 2-tert-butylphenyl group,3-tert-butylphenyl group, 4-tert-butylphenyl group,2,4-di-tert-butylphenyl group and 3,5-di-tert-butylphenyl group;

Of these, as the phenyl group substituted by an alkyl group having 1 to4 carbon atoms, p-tolyl group, m-tolyl group, o-tolyl group,4-trifluoromethylphenyl group and 4-butylphenyl group are preferable inview of the performance thereof as a material for an organicelectroluminescent device. P-tolyl group and m-tolyl group areespecially preferable because of inexpensiveness.

As specific examples of the phenyl group substituted by a halogen atom,there can be mentioned 3-chlorophenyl group, 4-chlorophenyl group,3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3-bromophenyl group,4-bromophenyl group, 3,4-dibromophenyl group and 3,5-dibromophenylgroup. Of these, 3-chlorophenyl group is preferable because of ease insynthesis.

As specific examples of the phenyl group substituted by an unsubstitutedor substituted phenyl group, there can be mentioned 4-biphenylyl group,3-biphenylyl group, 2-biphenylyl group, 2-methylbiphenyl-4-yl group,3-methylbiphenyl-4-yl group, 2′-methylbiphenyl-4-yl group,4′-methylbiphenyl-4-yl group, 2,2′-dimethylbiphenyl-4-yl group,2′,4′,6′-trimethylbiphenyl-4-yl group, 6-methylbiphenyl-3-yl group,5-methylbiphenyl-3-yl group, 2′-methylbiphenyl-3-yl group,4′-methylbiphenyl-3-yl group, 6,2′-dimethylbiphenyl-3-yl group,2′,4′,6′-trimethylbiphenyl-3-yl group, 5-methylbiphenyl-2-yl group,6-methylbiphenyl-2-yl group, 2′-methylbiphenyl-2-yl group,4′-methylbiphenyl-2-yl group, 6,2′-dimethylbiphenyl-2-yl group,2′,4′,6′-trimethylbiphenyl-2-yl group, 2-trifluoromethylbiphenyl-4-ylgroup, 3-trifluoromethylbiphenyl-4-yl group,2′-trifluoromethylbiphenyl-4-yl group, 4′-trifluoromethylbiphenyl-4-ylgroup, 6-trifluoromethylbiphenyl-3-yl group,5-trifluoromethylbiphenyl-3-yl group, 2′-trifluoromethylbiphenyl-3-ylgroup, 4′-trifluoromethylbiphenyl-3-yl group,5-trifluoromethylbiphenyl-2-yl group, 6-trifluoromethylbiphenyl-2-ylgroup, 2′-trifluormethylbiphenyl-2-yl group,4′-trifluoromethylbiphenyl-2-yl group, 3-ethylbiphenyl-4-yl group,4′-ethylbiphenyl-4-yl group, 2′,4′,6′-triethylbiphenyl-4-yl group,6-ethylbiphenyl-3-yl group, 4′-ethylbiphenyl-3-yl group,5-ethylbiphenyl-2-yl group, 4′-ethylbiphenyl-2-yl group,2′,4′,6′-triethylbiphenyl-2-yl group, 3-propylbiphenyl-4-yl group,4′-propylbiphenyl-4-yl group, 2′,4′,6′-tripropylbiphenyl-4-yl group,6-propylbiphenyl-3-yl group, 4′-propylbiphenyl-3-yl group,5-propylbiphenyl-2-yl group, 4′-propylbiphenyl-2-yl group,2′,4′,6′-tripropylbiphenyl-2-yl group, 3-isopropylbiphenyl-4-yl group,4′-isopropylbiphenyl-4-yl group, 2′,4′,6′-triisopropylbiphenyl-4-ylgroup, 6-isopropylbiphenyl-3-yl group, 4′-isopropylbiphenyl-3-yl group,5-isopropylbiphenyl-2-yl group, 4′-isopropylbiphenyl-2-yl group,2′,4′,6′-triisopropylbiphenyl-2-yl group, 3-butylbiphenyl-4-yl group,4′-butylbiphenyl-4-yl group, 2′,4′,6′-tributylbiphenyl-4-yl group,6-butylbiphenyl-3-yl group, 4′-butylbiphenyl-3-yl group,5-butylbiphenyl-2-yl group, 4′-butylbiphenyl-2-yl group,2′,4′,6′-tributylbiphenyl-2-yl group, 3-tert-butylbiphenyl-4-yl group,4′-tert-butylbiphenyl-4-yl group, 2′,4′,6′-tri-tert-butylbiphenyl-4-ylgroup, 6-tert-butylbiphenyl-3-yl group, 4′-tert-butylbiphenyl-3-ylgroup, 5-tert-butylbiphenyl-2-yl group, 4′-tert-butylbiphenyl-2-ylgroup, 2′,4′,6′-tri-tert-butylbiphenyl-2-yl group,1,1′:4′,1″-terphenyl-3-yl group, 1,1′:4′,1″-terphenyl-4-yl group,1,1′:3′,1″-terphenyl-3-yl group, 1,1′:3′,1″-terphenyl-4-yl group,1,1′:3′,1″-terphenyl-5′-yl group, 1,1′:2′,1″-terphenyl-3-yl group,1,1′:2′,1″-terphenyl-4-yl group, 1,1′:2′,1″-terphenyl-4′-yl group,2′-(2-pyridyl)biphenyl-2-yl group, 3′-(2-pyridyl)biphenyl-2-yl group,4′-(2-pyridyl)biphenyl-2-yl group, 2′-(3-pyridyl)biphenyl-2-yl group,3′-(3-pyridyl)biphenyl-2-yl group, 4′-(3-pyridyl)biphenyl-2-yl group,2′-(4-pyridyl)biphenyl-2-yl group, 3′-(4-pyridyl)biphenyl-2-yl group,4′-(4-pyridyl)biphenyl-2-yl group, 2′-(2-pyridyl)biphenyl-3-yl group,3′-(2-pyridyl)biphenyl-3-yl group, 4′-(2-pyridyl)biphenyl-3-yl group,2′-(3-pyridyl)biphenyl-3-yl group, 3′-(3-pyridyl)biphenyl-3-yl group,4′-(3-pyridyl)biphenyl-3-yl group, 2′-(4-pyridyl)biphenyl-3-yl group,3′-(4-pyridyl)biphenyl-3-yl group, 4′-(4-pyridyl)biphenyl-3-yl group,2′-(2-pyridyl)biphenyl-4-yl group, 3′-(2-pyridyl)biphenyl-4-yl group,4′-(2-pyridyl)biphenyl-4-yl group, 2′-(3-pyridyl)biphenyl-4-yl group,3′-(3-pyridyl)biphenyl-4-yl group, 4′-(3-pyridyl)biphenyl-4-yl group,2′-(4-pyridyl)biphenyl-4-yl group, 3′-(4-pyridyl)biphenyl-4-yl group and4′-(4-pyridyl) biphenyl-4-yl group.

Of these, as the phenyl group substituted by an unsubstituted orsubstituted phenyl group, 2-biphenylyl group, 3-biphenylyl group,4-biphenylyl group, 1,1′:3′,1″-terphenyl-5′-yl group,2′-(2-pyridyl)biphenyl-3-yl group, 3′-(2-pyridyl)biphenyl-3-yl group and4′-(2-pyridyl)biphenyl-3-yl group are preferable in view of theperformance thereof as a material for an organic electroluminescentdevice. 3-Biphenylyl group and 3′-(2-pyridyl)biphenyl-3-yl group areespecially preferable because of ease in synthesis.

As specific examples of the phenyl group which is substituted byunsubstituted or substituted pyrimidinyl groups, there can be mentioned2-(2-pyrimidinyl)phenyl group, 3-(2-pyrimidinyl)phenyl group,4-(2-pyrimidinyl)phenyl group, 2-(4-pyrimidinyl)phenyl group,3-(4-pyrimidinyl)phenyl group, 4-(4-pyrimidinyl)phenyl group,2-(5-pyrimidinyl)phenyl group, 3-(5-pyrimidinyl)phenyl group,4-(5-pyrimidinyl)phenyl group, 2-(4,6-dimethylpyrimidin-2-yl)phenylgroup, 3-(4,6-dimethylpyrimidin-2-yl)phenyl group,4-(4,6-dimethylpyrimidin-2-yl)phenyl group,2-(4,6-diphenylpyrimidin-2-yl)phenyl group,3-(4,6-diphenylpyrimidin-2-yl)phenyl group,4-(4,6-diphenylpyrimidin-2-yl)phenyl group,3-(4,6-di-p-tolylpyrimidin-2-yl)phenyl group,4-(4,6-di-m-tolylpyrimidin-2-yl)phenyl group,3-[4,6-bis(3,5-dimethylphenyl)pyrimidin-2-yl]phenyl group,4-[4,6-bis(2,6-dimethylphenyl)pyrimidin-2-yl]phenyl group,3-[4,6-bis(2-biphenylyl)pyrimidin-2-yl]phenyl group,4-[4,6-bis(3-biphenylyl)pyrimidin-2-yl]phenyl group,3-[4,6-di(2-naphtyl)pyrimidin-2-yl]phenyl group and4-[4,6-di(9-anthryl)pyrimidin-2-yl]phenyl group.

Of these, as the phenyl group substituted by an unsubstituted orsubstituted pyrimidinyl group, 4-(2-pyrimidinyl)phenyl group,4-(5-pyrimidinyl)phenyl group, 3-(4,6-dimethylpyrimidin-2-yl)phenylgroup, 4-(4,6-dimethylpyrimidin-2-yl)phenyl group,3-(4,6-diphenylpyrimidin-2-yl)phenyl group and4-(4,6-diphenylpyrimidin-2-yl)phenyl group are preferable in view of theperformance thereof as a material for an organic EL device.4-(2-Pyrimidinyl)phenyl group and 4-(5-pyrimidinyl)phenyl group areespecially preferable because of ease in synthesis.

As specific examples of the phenyl group unsubstituted or substitutedthiazolyl group, there can be mentioned 2-(2-thiazolyl)phenyl group,3-(2-thiazolyl)phenyl group, 4-(2-thiazolyl)phenyl group,2-(4-thiazolyl)phenyl group, 3-(4-thiazolyl)phenyl group,4-(4-thiazolyl)phenyl group, 2-(5-thiazolyl)phenyl group,3-(5-thiazolyl)phenyl group, 4-(5-thiazolyl)phenyl group,3-(2-thiazolyl)phenyl group, 4-(2-methylthiazol-5-yl)phenyl group,2-(4,5-dimethylthiazol-2-yl)phenyl group,3-(4,5-methylthiazol-2-yl)phenyl group, 4-(4,5-methylthiazol-2-yl)phenylgroup, 2-(2-phenylthiazol-4-yl)phenyl group,3-(2-phenylthiazol-4-yl)phenyl group, 4-(2-phenylthiazol-4-yl)phenylgroup, 4-(2-phenylthiazol-5-yl)phenyl group,2-(4,5-diphenylthiazol-2-yl)phenyl group,3-(4,5-diphenylthiazol-2-yl)phenyl group,4-(4,5-diphenylthiazol-2-yl)phenyl group, 2-(2-benzothiazolyl)phenylgroup, 3-(2-benzothiazolyl)phenyl group, 4-(2-benzothiazolyl)phenylgroup, 3-(2-naphthothiazolyl)phenyl group and4-(2-naphthothiazolyl)phenyl group.

Of these, as the phenyl group substituted by an unsubstituted orsubstituted thiazolyl group, 3-(4,5-diphenylthiazol-2-yl)phenyl group,4-(4,5-diphenylthiazol-2-yl)phenyl group and 4-(2-benzothiazolyl)phenylgroup are preferable in view of the performance thereof as a materialfor an organic electroluminescent device. 4-(2-Benzothiazolyl)phenylgroup is especially preferable because of ease in synthesis.

As specific examples of the phenyl group substituted by a pyridyl group,there can be mentioned 2-(2-pyridyl)phenyl group, 3-(2-pyridyl)phenylgroup, 4-(2-pyridyl)phenyl group, 2-(3-pyridyl)phenyl group,3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group,2-(4-pyridyl)phenyl group, 3-(4-pyridyl)phenyl group,4-(4-pyridyl)phenyl group, 4-phenyl-2-(2-pyridyl)phenyl group,5-phenyl-2-(2-pyridyl)phenyl group, 4-phenyl-3-(2-pyridyl)phenyl group,5-phenyl-3-(2-pyridyl)phenyl group, 6-phenyl-3-(2-pyridyl)phenyl group,3-phenyl-4-(2-pyridyl)phenyl group, 3-phenyl-2-(3-pyridyl)phenyl group,4-phenyl-2-(3-pyridyl)phenyl group, 4-phenyl-3-(3-pyridyl)phenyl group,5-phenyl-3-(3-pyridyl)phenyl group, 6-phenyl-3-(3-pyridyl)phenyl group,2-phenyl-4-(3-pyridyl)phenyl group, 4-phenyl-2-(4-pyridyl)phenyl group,4-phenyl-3-(4-pyridyl)phenyl group, 5-phenyl-3-(4-pyridyl)phenyl group,3-phenyl-4-(4-pyridyl)phenyl group, 3,4-di(2-pyridyl)phenyl group,3,4-di(3-pyridyl)phenyl group, 3,4-di(4-pyridyl)phenyl group,3-(2-pyridyl)-4-(3-pyridyl)phenyl group,3-(2-pyridyl)-4-(4-pyridyl)phenyl group,3-(3-pyridyl)-4-(2-pyridyl)phenyl group,3-(4-pyridyl)-4-(2-pyridyl)phenyl group, 3,5-di(2-pyridyl)phenyl group,3,5-di(3-pyridyl)phenyl group and 3,5-di(4-pyridyl)phenyl group.

Of these, as the phenyl group substituted by a pyridyl group,2-(2-pyridyl)phenyl group, 3-(2-pyridyl)phenyl group,4-(2-pyridyl)phenyl group, 3-(3-pyridyl)phenyl group,4-(3-pyridyl)phenyl group, 3-(4-pyridyl)phenyl group,4-(4-pyridyl)phenyl group, 5-phenyl-3-(2-pyridyl)phenyl group,5-phenyl-3-(3-pyridyl)phenyl group, 5-phenyl-3-(4-pyridyl)phenyl groupand 3,5-di(2-pyridyl)phenyl group are preferable in view of theperformance thereof as a material for an organic EL device.2-(2-Pyridyl)phenyl group, 3-(2-pyridyl)phenyl group,4-(3-pyridyl)phenyl group and 4-(4-pyridyl)phenyl group are especiallypreferable because of ease in synthesis.

As specific examples of the phenyl group substituted by aphenanthrolinyl group, there can be mentioned2-(2-phenanthrolinyl)phenyl group, 3-(2-phenanthrolinyl)phenyl group,4-(2-phenanthrolinyl)phenyl group, 2-(3-phenanthrolinyl)phenyl group,3-(3-phenanthrolinyl)phenyl group, 4-(3-phenanthrolinyl)phenyl group,2-(4-phenanthrolinyl)phenyl group, 3-(4-phenanthrolinyl)phenyl group and4-(4-phenanthrolinyl)phenyl group.

Of these, as the phenyl group substituted by a phenanthrolinyl group,3-(2-phenanthrolinyl)phenyl group, 4-(2-phenanthrolinyl)phenyl group,3-(3-phenanthrolinyl)phenyl group and 4-(3-phenanthrolinyl)phenyl groupare preferable in view of the performance thereof as a material for anorganic EL device. 4-(2-Phenanthrolinyl)phenyl group is especiallypreferable because of ease in synthesis.

In the general formula (2), a condensed aromatic hydrocarbon group nothaving a 16 group element represented by each Ar² must have a cyclicstructure which does not contain an element of 16 group of the PeriodicTable such as an oxygen atom or a sulfur atom. As specific examples ofsuch condensed aromatic hydrocarbon group, there can be mentioned1-naphthyl group, 2-naphthyl group, 2-anthryl group, 9-anthryl group,2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 1-pyrenylgroup, 2-pyrenyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolylgroup, 8-quinolyl group, 5-isoquinolyl group, 6-isoquinolyl group,7-isoquinolyl group and 8-quinolyl group.

Of these, as the condensed aromatic hydrocarbon group, 2-naphthyl group,9-anthryl group, 3-phenanthryl group and 6-quinolyl group are preferablein view of the performance thereof as a material for an organicelectroluminescent device. 6-Quinolyl group is especially preferablebecause of ease in synthesis.

In the general formula (3), Ar³ represents a phenyl group, a pyridylgroup or a pyrimidinyl group.

In the general formula (3), Ar⁴ represents an unsubstituted orsubstituted aromatic hydrocarbon group having 2 to 4 rings, andincludes, for example, an unsubstituted or substituted naphthyl group,an unsubstituted or substituted anthryl group, an unsubstituted orsubstituted phenanthryl group, an unsubstituted or substituted fluorenylgroup, an unsubstituted or substituted benzofluorenyl group, anunsubstituted or substituted pyrenyl group and an unsubstituted orsubstituted triphenylenyl group.

As specific examples of the unsubstituted or substituted naphthyl grouprepresented by Ar⁴ in the general formula (3), there can be mentioned1-naphthyl group and 2-naphthyl group; and naphthyl groups substitutedby an alkyl group having 1 to 4 carbon atoms, such as4-methylnaphthalen-1-yl group, 4-trifluoromethylnaphthalen-1-yl group,4-ethylnaphthalen-1-yl group, 4-propylnaphthalen-1-yl group,4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group,5-methylnaphthalen-1-yl group, 5-trifluoromethylnaphthalen-1-yl group,5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group,5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group,6-methylnaphthalen-2-yl group, 6-trifluoromethylnaphthalen-2-yl group,6-ethylnaphthalen-2-yl group, 6-propylnaphthalen-2-yl group,6-butylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group,7-methylnaphthalen-2-yl group, 7-trifluoromethylnaphthalen-2-yl group,7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group,7-butylnaphthalen-2-yl group and 7-tert-butylnaphthalen-2-yl group.

Of these unsubstituted or substituted naphthyl groups, l-naphthyl group,4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group,5-methylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group,2-naphthyl group, 6-methylnaphthalen-2-yl group,6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group and7-tert-butylnaphthalen-2-yl group are preferable in view of theperformance thereof as a material for an organic electroluminescentdevice. 1-Naphthyl group is especially preferable because of ease insynthesis.

As specific examples of the unsubstituted or substituted anthryl grouprepresented by Ar⁴, there can be mentioned 1-anthryl group, 2-anthrylgroup and 9-anthryl group; and anthryl groups substituted by an alkylgroup having 1 to 4 carbon atoms or a phenyl group, such as2-methylanthracen-1-yl group, 3-methylanthracen-1-yl group,4-methylanthracen-1-yl group, 9-methylanthracen-1-yl group,10-methylanthracen-1-yl group, 2-phenylanthracen-1-yl group,3-phenylanthracen-1-yl group, 4-phenylanthracen-1-yl group,5-phenylanthracen-1-yl group, 6-phenylanthracen-1-yl group,7-phenylanthracen-1-yl group, 8-phenylanthracen-1-yl group,9-phenylanthracen-1-yl group, 10-phenylanthracen-1-yl group,1-methylanthracen-2-yl group, 3-methylanthracen-2-yl group,4-methylanthracen-2-yl group, 9-methylanthracen-2-yl group,10-methylanthracen-2-yl group, 1-phenylanthracen-2-yl group,3-phenylanthracen-2-yl group, 4-phenylanthracen-2-yl group,5-phenylanthracen-2-yl group, 6-phenylanthracen-2-yl group,7-phenylanthracen-2-yl group, 8-phenylanthracen-2-yl group,9-phenylanthracen-2-yl group, 10-phenylanthracen-2-yl group,2-methylanthracen-9-yl group, 3-methylanthracen-9-yl group,4-methylanthracen-9-yl group, 10-methylanthracen-9-yl group,2-phenylanthracen-9-yl group, 3-phenylanthracen-9-yl group,4-phenylanthracen-9-yl group, 5-phenylanthracen-9-yl group,6-phenylanthracen-9-yl group, 7-phenylanthracen-9-yl group,8-phenylanthracen-9-yl group and 10-phenylanthracen-9-yl group.

Of these unsubstituted or substituted anthryl groups, 1-anthryl group,2-anthryl group, 9-anthryl group, and 10-phenylanthracen-9-yl group arepreferable in view of the performance thereof as a material for anorganic electroluminescent device. 9-Anthryl group is especiallypreferable because of ease in synthesis.

As specific examples of the unsubstituted or substituted phenanthrylgroup represented by Ar⁴, there can be mentioned 1-phenanthryl group,2-phenanthryl group, 3-phenanthryl group and 4-phenanthryl group and9-phenanthryl group; and phenanthryl groups substituted by an alkylgroup having 1 to 4 carbon atoms or a phenyl group, such as2-phenylphenanthren-1-yl group, 3-phenylphenanthren-1-yl group,4-phenylphenanthren-1-yl group, 9-phenylphenanthren-1-yl group,1-phenylphenanthren-2-yl group, 3-phenylphenanthren-2-yl group,4-phenylphenanthren-2-yl group, 9-phenylphenanthren-2-yl group,1-phenylphenanthren-3-yl group, 2-phenylphenanthren-3-yl group,4-phenylphenanthren-3-yl group, 9-phenylphenanthren-3-yl group,1-phenylphenanthren-4-yl group, 2-phenylphenanthren-4-yl group,3-phenylphenanthren-4-yl group, 9-phenylphenanthren-4-yl group,1-phenylphenanthren-9-yl group, 2-phenylphenanthren-9-yl group,3-phenylphenanthren-9-yl group and 4-phenylphenanthren-9-yl group.

Of these unsubstituted or substituted phenanthryl groups, 1-phenanthrylgroup, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group and9-phenanthryl group are preferable in view of the performance thereof asa material for an organic electroluminescent device. 9-Phenanthryl groupis especially preferable because of ease in synthesis.

As specific examples of the unsubstituted or substituted fluorenyl grouprepresented by Ar⁴, there can be mentioned unsubstituted fluorenylgroup; and fluorenyl groups substituted by an alkyl group having 1 to 4carbon atoms or a phenyl group, such as 9,9-dimethylfluoren-1-yl group,9,9-dimethylfluoren-2-yl group, 9,9-dimethylfluoren-3-yl group,9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-1-yl group,9,9-diphenylfluoren-2-yl group, 9,9-diphenylfluoren-3-yl group and9,9-diphenylfluoren-4-yl group.

Of these unsubstituted or substituted fluorenyl groups,9,9-dimethylfluoren-2-yl group, 9,9-dimethylfluoren-3-yl group and9,9-diphenylfluoren-2-yl group are preferable in view of the performancethereof as a material for an organic electroluminescent device.9,9-Dimethylfluoren-2-yl group is especially preferable because of easein synthesis.

As specific examples of the unsubstituted or substituted benzofluorenylgroup represented by Ar⁴, there can be mentioned unsubstitutedbenzofluorenyl group; and benzofluorenyl groups substituted by an alkylgroup having 1 to 4 carbon atoms or a phenyl group, such as9,9-dimethylbenzo[a]fluoren-3-yl group, 9,9-dimethylbenzo[a]fluoren-4-ylgroup, 9,9-dimethylbenzo[a]fluoren-5-yl group,9,9-dimethylbenzo[a]fluoren-6-yl group, 9,9-dimethylbenzo[a]fluoren-7-ylgroup, 9,9-dimethylbenzo[a]fluoren-8-yl group,9,9-dimethylbenzo[b]fluoren-1-yl group, 9,9-dimethylbenzo[b]fluoren-4-ylgroup, 9,9-dimethylbenzo[b]fluoren-5-yl group,9,9-dimethylbenzo[b]fluoren-6-yl group, 9,9-dimethylbenzo[b]fluoren-7-ylgroup, 9,9-dimethylbenzo[b]fluoren-8-yl group,9,9-dimethylbenzo[c]fluoren-1-yl group, 9,9-dimethylbenzo[c]fluoren-2-ylgroup, 9,9-dimethylbenzo[c]fluoren-5-yl group,9,9-dimethylbenzo[c]fluoren-6-yl group, 9,9-dimethylbenzo[c]fluoren-7-ylgroup, 9,9-dimethylbenzo[c]fluoren-8-yl group,9,9-diphenylbenzo[a]fluoren-3-yl group, 9,9-diphenylbenzo[a]fluoren-4-ylgroup, 9,9-diphenylbenzo[a]fluoren-5-yl group,9,9-diphenylbenzo[a]fluoren-6-yl group, 9,9-diphenylbenzo[a]fluoren-7-ylgroup, 9,9-diphenylbenzo[a]fluoren-8-yl group,9,9-diphenylbenzo[b]fluoren-1-yl group, 9,9-diphenylbenzo[b]fluoren-4-ylgroup, 9,9-diphenylbenzo[b]fluoren-5-yl group,9,9-diphenylbenzo[b]fluoren-6-yl group, 9,9-diphenylbenzo[b]fluoren-7-ylgroup, 9,9-diphenylbenzo[b]fluoren-8-yl group,9,9-diphenylbenzo[c]fluoren-1-yl group, 9,9-diphenylbenzo[c]fluoren-2-ylgroup, 9,9-diphenylbenzo[c]fluoren-5-yl group,9,9-diphenylbenzo[c]fluoren-6-yl group, 9,9-diphenylbenzo[c]fluoren-7-ylgroup and 9,9-diphenylbenzo[c]fluoren-8-yl group.

Of these unsubstituted or substituted benzofluorenyl groups,9,9-dimethylbenzo[a]fluoren-6-yl group, 9,9-dimethylbenzo[a]fluoren-7-ylgroup, 9,9-dimethylbenzo[b]fluoren-6-yl group,9,9-dimethylbenzo[b]fluoren-7-yl group, 9,9-dimethylbenzo[c]fluoren-2-ylgroup, 9,9-dimethylbenzo[c]fluoren-6-yl group and9,9-dimethylbenzo[c]fluoren-7-yl group are preferable in view of theperformance thereof as a material for an organic electroluminescentdevice. 9,9-Dimethylbenzo[c]fluoren-2-yl group is especially preferablebecause of ease in synthesis.

As specific examples of the unsubstituted or substituted pyrenyl grouprepresented by Ar⁴, there can be mentioned 1-pyrenyl group,6-phenylpyren-1-yl group, 7-phenylpyren-1-yl group, 8-phenylpyren-1-ylgroup, 2-pyrenyl group, 6-phenylpyren-2-yl group, 7-phenylpyren-2-ylgroup and 8-phenylpyren-2-yl group.

Of these unsubstituted or substituted pyrenyl groups, 1-pyrenyl groupand 2-pyrenyl group are preferable in view of the performance thereof asa material for an organic electroluminescent device. 2-Pyrenyl group isespecially preferable because of ease in synthesis.

As specific examples of the unsubstituted or substituted triphenylenylgroup represented by Ar⁴, 1-triphenylenyl group and 2-triphenylenylgroup are mentioned.

In the general formulae (3) and (11), X represents a phenylene group ora pyridylene group.

The compound represented by the general formula (11) can be produced,for example, by a process described in JP 2008-280330 A, paragraphs[0061]-[0076]. As specific examples of the compound of the formulae(11), the following compounds (11-1) through (11-79) are mentioned, butthe compounds used in the present invention should not be limitedthereto.

A representative category of the azine compound according to the presentinvention is a compound represented by the above-mentioned generalformula (1c). The compound of the formula (1c) has substituents,represented by the following general formula (13a), on a benzene ring ofthe compound of the formula (1c).

wherein Ar⁵ and Ar⁶ represent a phenyl group or a pyridyl group, and Z³represents a carbon or nitrogen atom, provided that, when Z³ representsa carbon atom, Ar⁵ and Ar⁶ cannot be simultaneously a phenyl group. Asspecific examples of the substituents of the formula (13a), thefollowing groups (13a-1) through (13a-19) are mentioned, but thesubstituents of the formula (13a) used in the present invention shouldnot be limited thereto.

The metal group represented by M in the formulae (7) and (11) is notparticularly limited, and those which are conventionally used in thegeneral coupling reaction can be used. The metal group includes, forexample, Li, Na, MgCl, MgBr, MgI, CuCl, CuBr, CuI, AlCl₂, AlBr₂,Al(Me)₂, Al(Et)₂, Al(^(i)Bu)₂, Sn(Me)₃, Sn(Bu)₃, ZnR² where ZnR²includes, for example, ZnCl, ZnBr and ZnI.

Of these metal groups, ZnCl is preferable in view of high reactionyield. ZnCl coordinated with tetramethylethylenediamine (TMADA) isespecially preferable.

The hetero atom group represented by M includes, for example, Si(Ph)₃,SnF₃, and B(OR²)₂ where B(OR¹)₂ includes, for example, B(OMe)₂,B(O^(i)Pr)₂, B(OBu)₂ and B(OPh)₂. The two R¹s in B(OR¹)₂ may form a ringtogether with the oxygen atom and the boron atom, thus, B(OR¹)₂ formsthe following groups (I) to (VI), for example. Of these groups (I) to(VI), group (II) is preferable in view of high reaction yield.

The azine derivative of the formula (1a) according to the presentinvention can be prepared by a process comprising a step 1 involving thefollowing reaction scheme.

In the reaction scheme of step 1, each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; and each Ar² representsa substituted phenyl group or a condensed aromatic hydrocarbon group nothaving a 16 group element, provided that a 1,3,5-trimethylphenyl groupis excluded from Ar². Each Y¹ represents a chlorine, bromine or iodineatom. M represents a metal group or a hetero atom group.

The step 1 is a step of reacting the compound of formula (6) with thecompound of formula (7) in the presence of a palladium catalyst and inthe presence or absence of a base to prepare the cyclic azine derivative(1a) according to the present invention. This coupling reaction can beeffected by adopting conventional reaction conditions, which are adoptedin the conventional coupling reactions such as, for example,Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction andStille reaction. The target compound can be obtained with a high yieldby adopting such reaction conditions.

The palladium catalyst used in the step 1 includes, for example,palladium salts such as palladium chloride, palladium acetate, palladiumtrifluoroacetate and palladium nitrate; and complex compounds such asπ-allylpalladium chloride dimmer, palladium acetylacetonate,tris(dibenzylideneacetone)dipalladium,dichlorobis(triphenylphosphine)palladium,tetrakis(triphenylphosphine)palladium anddichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium.

Of these, palladium complex compounds having a tertiary phosphine as aligand are preferable because of high reaction yield. Palladium complexcompounds having a triphenylphosphine as a ligand are especiallypreferable because they are readily available and give high reactionyield.

The molar ratio of the palladium catalyst to the compound of formula (6)is preferably in the range of 1:200 to 1:2, and more preferably 1:50 to1:10 because of high reaction yield.

Palladium complex compounds having a tertiary phosphine as a ligand canalso be synthesized in a reaction system containing a palladium salt ora palladium complex compound and a tertiary phosphine added therein.

As specific examples of the tertiary phosphine used, there can bementioned triphenylphosphine, trimethylphosphine, tributylphosphine,tri(tert-butyl)phosphine, tricyclohexylphosphine,tert-butyldiphenylphosphine,9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene,2-(diphenylphosphino)-2′-(N,N-dimethylamino)biphenyl,2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)-biphenyl,bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane,1,3-bis(diphenylphosphino)-propane, 1,4-bis(diphenylphosphino)butane,1,1′-bis(diphenylphosphino)ferrocene, tri-(2-furyl)phosphine,tri-(o-tolyl)phosphine, tris(2,5-xylyl)phosphine,(±)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl and2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl.

Of these, triphenylphosphine is preferable in view of ease inavailability and high reaction yield.

The molar ratio of the tertiary phosphine to the palladium salt or thepalladium complex compound is preferably in the range of 1:10 to 10:1,and more preferably 1:2 to 5:1 because of high reaction yield.

The molar ratio of the compound of formula (6) to the compound offormula (7), which are used in the step 1, is preferably in the range of1:2 to 5:1, and more preferably 1:2 to 2:1 because of high yield.

In the case when the step 1 is carried out according to Suzuki-Miyaurareaction using the compound of the formula (7) wherein M is B(OR¹)₂, thereaction yield can be enhanced by carrying out the reaction in thepresence of a base.

The base capable of being used in the step 1 includes, for example,sodium hydroxide, potassium hydroxide, sodium carbonate, potassiumcarbonate, lithium carbonate, cesium carbonate, potassium phosphate,sodium phosphate, sodium fluoride, potassium fluoride and cesiumfluoride. Of these, cesium carbonate is preferable because of highreaction yield. The molar ratio of the base to the compound of formula(7) is preferably in the range of 1:2 to 10:1, and more preferably 1:1to 3:1 because of high reaction yield.

The reaction in the step 1 can be effected in a reaction medium. Thereaction medium used in the step 1 includes, for example, water,dimethylsulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene,diethyl ether, ethanol, methanol and xylene. These reaction mediums maybe used either alone or in combination. Of these, toluene andtetrahydrofuran are preferable because of high reaction yield.

The reaction in the step 1 can be effected at a temperatureappropriately chosen in a range of 0° C. to 150° C. A temperature of 40°C. to 110° C. is especially preferable because of high reaction yield.

The cyclic azine compound of formula (1a) according to the presentinvention can be obtained by conducting the conventional treatingprocedure after completion of the step 1. If desired, the producedcompound is purified by, for example, recrystallization, columnchromatography or sublimation.

The cyclic azine compound of formula (1a) according to the presentinvention can also be prepared by a process comprising a step 2involving the following reaction scheme.

In the reaction scheme of step 2, each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; and each Ar² representsa substituted phenyl group or a condensed aromatic hydrocarbon group nothaving a 16 group element, provided that a 1,3,5-trimethylphenyl groupis excluded from Ar². Y¹ represents a chlorine, bromine or iodine atom.Each R¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbonatoms or a phenyl group; and groups R¹ in the two —B(OR¹) groups may bethe same or different, and two groups R¹ in each of the two —B(OR¹)groups may form a ring together with the oxygen atoms and the boronatom.

The step 2 is a step of reacting the compound of formula (8) with thecompound of formula (9) in the presence of a palladium catalyst and abase to prepare the cyclic azine compound of formula (1a) according tothe present invention. This coupling reaction can be effected byadopting conventional reaction conditions adopted in the conventionalSuzuki-Miyaura reaction. The target compound can be obtained with a highyield by adopting such reaction conditions.

The palladium catalyst used in the step 2 includes, for example,palladium salts and complex compounds, which are exemplified with regardto the palladium catalyst used in the step 1. Of these catalysts,palladium complex compounds having a tertiary phosphine as a ligand arepreferable because of high reaction yield. Palladium complex compoundshaving a triphenylphosphine as a ligand are especially preferable inview of ease in availability and high reaction yield.

The molar ratio of the palladium catalyst to the compound of formula (8)is preferably in the range of 1:200 to 1:2, and more preferably 1:50 to1:10 because of high reaction yield.

Palladium complex compounds having a tertiary phosphine as a ligand canalso be synthesized in a reaction system containing a palladium salt ora palladium complex compound and a tertiary phosphine added therein.

As specific examples of the tertiary phosphine used, those which areexemplified with regard to the step 1 can be mentioned. Of thesetertiary phosphines, triphenylphosphine is preferable in view of ease inavailability and high reaction yield.

The molar ratio of the tertiary phosphine to the palladium salt or thepalladium complex compound is preferably in the range of 1:10 to 10:1,and more preferably 1:2 to 5:1 because of high reaction yield.

It is essential to carry out the step 2 in the presence of a base. Thebase used in the step 2 includes, for example, sodium hydroxide,potassium hydroxide, sodium carbonate, potassium carbonate, lithiumcarbonate, cesium carbonate, potassium phosphate, sodium phosphate,sodium fluoride, potassium fluoride and cesium fluoride. Of these,cesium carbonate is preferable because of high reaction yield. The molarratio of the base to the compound of formula (8) is preferably in therange of 1:2 to 10:1, and more preferably 1:1 to 4:1 because of highreaction yield.

The molar ratio of the compound of formula (8) to the compound offormula (9), which are used in the step 2, is preferably in the range of1:10 to 2:1, and more preferably 1:2 to 1:4 because of high yield.

The reaction in the step 2 can be effected in a reaction medium. Thereaction medium used in the step 2 includes, for example, water,dimethylsulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene,diethyl ether, ethanol, methanol and xylene. These reaction mediums maybe used either alone or in combination. Of these, a mixed medium oftoluene with water is preferable because of high reaction yield.

The reaction in the step 2 can be effected at a temperatureappropriately chosen in a range of 0° C. to 150° C. A temperature of 40°C. to 110° C. is especially preferable because of high reaction yield.

The cyclic azine compound of formula (1a) according to the presentinvention can be obtained by conducting the conventional treatingprocedure after completion of the step 2. If desired, the producedcompound is purified by, for example, recrystallization, columnchromatography or sublimation.

The compound of formula (8), which is a raw material for preparing thecyclic azine compound of formula (1a) according to the present inventionby the step 2, can be prepared, for example, by a process comprising astep 3 involving the following reaction scheme.

In the reaction scheme of step 3, each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group; each R¹ represents ahydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenylgroup; and groups R¹ in the two —B(OR¹) groups may be the same ordifferent, and two groups R¹ in each of the two —B(OR¹) groups may forma ring together with the oxygen atoms and the boron atom. Y¹ representsa chlorine, bromine or iodine atom.

The step 3 is a step of reacting a compound of the formula (6) with aborane compound of the general formula (16) or a diborane compound ofthe general formula (17) in the presence of a palladium catalyst and abase to give the compound of the formula (8) used in the step 2. Thisreaction can be effected with a high reaction yield of the targetcompound by adopting reaction conditions, which are described in TheJournal of Organic Chemistry, vol. 60, 7508-7510, 1995, or The Journalof Organic Chemistry, vol. 65, 164-168, 2000.

The palladium catalyst used in the step 3 includes, for example,palladium salts and complex compounds, which are exemplified with regardto the palladium catalyst used in the step 1. Of these catalysts,palladium complex compounds having a tertiary phosphine as a ligand arepreferable because of high reaction yield. Palladium complex compoundshaving a triphenylphosphine as a ligand are especially preferable inview of ease in availability and high reaction yield.

The molar ratio of the palladium catalyst to the compound of formula (6)is preferably in the range of 1:200 to 1:2, and more preferably 1:50 to1:10 because of high reaction yield.

Palladium complex compounds having a tertiary phosphine as a ligand canalso be synthesized in a reaction system containing a palladium salt ora palladium complex compound and a tertiary phosphine added therein.

As specific examples of the tertiary phosphine used, those which areexemplified with regard to the step 1 can be mentioned. Of thesetertiary phosphines, triphenylphosphine is preferable in view of ease inavailability and high reaction yield.

The molar ratio of the tertiary phosphine to the palladium salt or thepalladium complex compound is preferably in the range of 1:10 to 10:1,and more preferably 1:2 to 5:1 because of high reaction yield.

It is essential to carry out the step 3 in the presence of a base. Thebase used in the step 3 includes, for example, sodium hydroxide,potassium hydroxide, sodium carbonate, potassium carbonate, lithiumcarbonate, cesium carbonate, potassium phosphate, sodium phosphate,sodium fluoride, potassium fluoride and cesium fluoride. Of these,cesium carbonate is preferable because of high reaction yield. The molarratio of the base to the compound of formula (6) is preferably in therange of 1:2 to 10:1, and more preferably 2:1 to 4:1 because of highreaction yield.

The molar ratio of the borane compound of formula (16) or the diboranecompound of formula (17) to the compound of formula (6), which are usedin the step 3, is preferably in the range of 1:1 to 5:1, and morepreferably 2:1 to 3:1 because of high yield.

The reaction in the step 3 can be effected in a reaction medium. Thereaction medium used in the step 3 includes, for example, water,dimethylsulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene,diethyl ether, ethanol, methanol and xylene. These reaction mediums maybe used either alone or in combination. Of these, tetrahydrofuran ispreferable because of high reaction yield.

The reaction in the step 3 can be effected at a temperatureappropriately chosen in a range of 0° C. to 150° C. A temperature of 40°C. to 80° C. is especially preferable because of high reaction yield.

The compound of formula (8) obtained in the step 3 may be isolated aftercompletion of the reaction. Alternatively the compound of formula (8)may be used as a raw material in the step (2).

The cyclic azine compound of the formula (1b) according to the presentinvention can also be prepared by a process comprising a step 4involving the following reaction scheme.

In the reaction scheme in the step 4, each Ar¹ represents an aromaticgroup, which is unsubstituted or substituted by an alkyl group having 1to 4 carbon atoms, a phenyl group or a pyridyl group; and Ar⁴ representsa substituted or unsubstituted aromatic hydrocarbon group having 2 to 4rings. Z¹ represents a carbon or nitrogen atom; and Y represents achlorine, bromine or iodine atom. Ar³ represents a phenyl group, apyridyl group or a pyrimidinyl group. X represents a phenylene group ora pyridylene group. p represents an integer of 0 to 2 provided that,when p is 2, the two Xs may be the same or different. M represents ametal group or a hetero atomic group.

The step 4 is a step of reacting the compound of formula (10) with thecompound of formula (11) in the presence of a palladium catalyst and inthe presence or absence of a base to prepare the cyclic azine compoundof formula (1b) according to the present invention. This reaction can beeffected by adopting conventional reaction conditions, which are adoptedin the conventional coupling reactions such as, for example,Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction andStille reaction. The target compound can be obtained with a high yieldby adopting such reaction conditions.

The palladium catalyst used in the step 4 includes, for example,palladium salts and complex compounds, which are exemplified with regardto the palladium catalyst used in the step 1. Of these catalysts,palladium complex compounds having a tertiary phosphine as a ligand arepreferable because of high reaction yield. Palladium complex compoundshaving a triphenylphosphine as a ligand are especially preferable inview of ease in availability and high reaction yield.

Palladium complex compounds having a tertiary phosphine as a ligand canalso be synthesized in a reaction system containing a palladium salt ora palladium complex compound and a tertiary phosphine added therein.

As specific examples of the tertiary phosphine used, those which areexemplified with regard to the step 1 can be mentioned. Of thesetertiary phosphines, triphenylphosphine is preferable in view of ease inavailability and high reaction yield.

The molar ratio of the tertiary phosphine to the palladium salt or thepalladium complex compound is preferably in the range of 1:10 to 10:1,and more preferably 1:2 to 5:1 because of high reaction yield.

The base capable of being used in the step 2 includes, for example,sodium hydroxide, potassium hydroxide, sodium carbonate, potassiumcarbonate, lithium carbonate, cesium carbonate, potassium phosphate,sodium phosphate, sodium fluoride, potassium fluoride and cesiumfluoride. Of these, cesium carbonate is preferable because of highreaction yield. The molar ratio of the base to the compound of formula(11) is preferably in the range of 1:2 to 10:1, and more preferably 1:1to 3:1 because of high reaction yield.

The molar ratio of the compound of formula (10) to the compound offormula (11), which are used in the step 4, is preferably in the rangeof 1:2 to 5:1, and more preferably 1:2 to 2:1 because of high yield.

The reaction medium used in the step 4 includes, for example, water,dimethylsulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene,diethyl ether, ethanol, methanol and xylene. These reaction mediums maybe used either alone or in combination. Of these, a mixed medium oftoluene with ethanol is preferable because of high reaction yield.

The reaction in the step 4 can be effected at a temperatureappropriately chosen in a range of 0° C. to 150° C. A temperature of 40°C. to 80° C. is especially preferable because of high reaction yield.

The cyclic azine compound of formula (1b) according to the presentinvention can be obtained by conducting the conventional treatingprocedure after completion of the step 4. If desired, the producedcompound is purified by, for example, recrystallization, columnchromatography or sublimation.

The compound of formula (10) used for the preparation of the cyclicazine compound of formula (1b) according to the present invention can beprepared by a process comprising a step 5 involving the followingreaction scheme.

In the reaction scheme in the step 5, each Ar¹ represents an aromaticgroup, which is unsubstituted or substituted by an alkyl group having 1to 4 carbon atoms, a phenyl group or a pyridyl group; and Ar⁴ representsa substituted or unsubstituted aromatic hydrocarbon group having 2 to 4rings. Z¹ represents a carbon or nitrogen atom; and Y¹ and Y² representa chlorine, bromine or iodine atom. M represents a metal group or ahetero atomic group.

The step 5 is a step of reacting the compound of formula (18) with thecompound of formula (19) in the presence of a palladium catalyst and inthe presence or absence of a base to prepare the compound of formula(10) used for the preparation of the cyclic azine compound of formula(1b) according to the present invention. This reaction can be effectedby adopting conventional reaction conditions, which are adopted in theconventional coupling reactions such as, for example, Suzuki-Miyaurareaction, Negishi reaction, Tamao-Kumada reaction and Stille reaction.The target compound can be obtained with a high yield by adopting suchreaction conditions.

The palladium catalyst used in the step 5 includes, for example,palladium salts and complex compounds, which are exemplified with regardto the palladium catalyst used in the step 1. Of these catalysts,palladium complex compounds having a tertiary phosphine as a ligand arepreferable because of high reaction yield. Palladium complex compoundshaving a triphenylphosphine as a ligand are especially preferable inview of ease in availability and high reaction yield.

Palladium complex compounds having a tertiary phosphine as a ligand canalso be synthesized in a reaction system containing a palladium salt ora palladium complex compound and a tertiary phosphine added therein.

As specific examples of the tertiary phosphine used, those which areexemplified with regard to the step 1 can be mentioned. Of thesetertiary phosphines, triphenylphosphine is preferable in view of ease inavailability and high reaction yield.

The molar ratio of the tertiary phosphine to the palladium salt or thepalladium complex compound is preferably in the range of 1:10 to 10:1,and more preferably 1:2 to 5:1 because of high reaction yield.

The base capable of being used in the step 5 includes, for example,those which are exemplified with regard to the step 1. Of these,potassium carbonate is preferable because of high reaction yield. Themolar ratio of the base to the compound of formula (19) is preferably inthe range of 1:1 to 10:1, and more preferably 2:1 to 3:1 because of highreaction yield.

The molar ratio of the compound of formula (18) to the compound offormula (19), which are used in the step 5, is preferably in the rangeof 1:2 to 5:1, and more preferably 1:2 to 2:1 because of high yield.

The reaction medium used in the step 5 includes, for example, water,dimethylsulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene,diethyl ether, ethanol, methanol and xylene. These reaction mediums maybe used either alone or in combination. Of these, a mixed medium oftoluene with ethanol is preferable because of high reaction yield.

The reaction in the step 5 can be effected at a temperatureappropriately chosen in a range of 0° C. to 150° C. A temperature of 40°C. to 80° C. is especially preferable because of high reaction yield.

The compound of formula (10) can be obtained by conducting theconventional treating procedure after completion of the step 5. Ifdesired, the produced compound is purified by, for example,recrystallization, column chromatography or sublimation.

The cyclic azine compound of formula (1c) according to the presentinvention can be prepared, for example, by a process comprising a step 6involving the following reaction scheme.

In the reaction scheme of step 6, each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group. Z² represents a carbonor nitrogen atom. Each R¹ represents a hydrogen atom, an alkyl grouphaving 1 to 4 carbon atoms or a phenyl group; and groups R¹ in the two—B(OR¹)₂ groups may be the same or different, and two groups R¹ in eachof the two —B(OR¹)₂ groups may form a ring together with the oxygenatoms and the boron atom. Each Ar⁵ and each Ar⁶ represent a phenyl groupor a pyridyl group; and each Z³ represents a carbon or nitrogen atom,provided that, when each Z³ represents a carbon atom, each Ar⁵ and eachAr⁶ cannot be simultaneously a phenyl group. Y¹ represents a chlorine,bromine or iodine atom.

The compound of formula (13) can be prepared by a process described in,for example, Dalton Trans., 4659-4665, 2007; JP 2002-363161 A; or theprocess in Experiment Examples 42 and 43, described below.

As specific examples of the compound of formula (13), the followingcompounds 13-1 through 13-19 are mentioned, but the compound of formula(13) used in the present invention is not limited thereto. In thefollowing chemical formulae of the compounds 13-1 through 13-19, Y¹represents a chlorine, bromine or iodine atom.

The step 6 is a step of reacting a compound of the formula (13) with acompound of the formula (12) in the presence of a palladium catalyst anda base to give the cyclic azine compound of formula (1c) according tothe present invention. This reaction can be effected with a highreaction yield of the target compound by adopting reaction conditions,adopted in the conventional Suzuki-Miyaura reaction. The target compoundcan be obtained with a high yield by adopting such reaction conditions.

The palladium catalyst used in the step 6 includes, for example,palladium salts and complex compounds, which are exemplified with regardto the palladium catalyst used in the step 1. Of these catalysts,palladium complex compounds having a tertiary phosphine as a ligand arepreferable because of high reaction yield. Palladium complex compoundshaving a triphenylphosphine as a ligand are especially preferable inview of ease in availability and high reaction yield.

The amount of the palladium catalyst used in the step 6 is notparticularly limited, provided that it is a catalytical amount. Themolar ratio of the palladium catalyst to the compound of formula (12) ispreferably in the range of 1:50 to 1:10.

Palladium complex compounds having a tertiary phosphine as a ligand canalso be synthesized in a reaction system containing a palladium salt ora palladium complex compound and a tertiary phosphine added therein.

As specific examples of the tertiary phosphine used, those which areexemplified with regard to the step 1 can be mentioned. Of thesetertiary phosphines, triphenylphosphine is preferable in view of ease inavailability and high reaction yield.

The molar ratio of the tertiary phosphine to the palladium salt or thepalladium complex compound is preferably in the range of 1:10 to 10:1,and more preferably 1:2 to 5:1 because of high reaction yield.

It is essential to carry out the step 6 in the presence of a base. Thebase used in the step 6 includes, for example, sodium hydroxide,potassium hydroxide, sodium carbonate, potassium carbonate, lithiumcarbonate, cesium carbonate, potassium acetate, sodium acetate,potassium phosphate, sodium phosphate, sodium fluoride, potassiumfluoride and cesium fluoride. Of these, sodium carbonate is preferablebecause of high reaction yield. The molar ratio of the base to thecompound of formula (12) is not particularly limited, but is preferablyin the range of 1:2 to 10:1, and more preferably 1:1 to 3:1 because ofhigh reaction yield.

The molar ratio of the compound of formula (13) to the compound offormula (12), which are used in the step 6, is not particularly limited,but is preferably in the range of 1:1 to 5:1, and more preferably 2:1 to3:1 because of high yield.

The reaction in the step 6 can be effected in a reaction medium. Thereaction medium used includes, for example, water, dimethylsulfoxide,dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether,ethanol, methanol and xylene. These reaction mediums may be used eitheralone or in combination. Of these, a mixed medium comprised of tolueneand water is preferable because of high reaction yield.

The cyclic azine compound of formula (1c) according to the presentinvention can be obtained by conducting the conventional treatingprocedure after completion of the step 6. If desired, the producedcompound is purified by, for example, recrystallization, columnchromatography or sublimation.

The compound of formula (12) used as a raw material for the preparationof the cyclic azine derivative of formula (1c) of the present inventionin the step 6 can be prepared by a process comprising a step 7 involvingthe following reaction scheme. Specific examples of the step 7 areshown, for example, in Experiment Examples 34 to 36.

In the reaction scheme of step 7, each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group. Z² represents a carbonor nitrogen atom. Each R¹ represents a hydrogen atom, an alkyl grouphaving 1 to 4 carbon atoms or a phenyl group; and groups R¹ in the two—B(OR¹)₂ groups may be the same or different, and two groups R¹ in eachof the two —B(OR¹)₂ groups may form a ring together with the oxygenatoms and the boron atom. Y¹ represents a chlorine, bromine or iodineatom.

The compound of formula (20) can be prepared by a process specificallydescribed in, for example, Experiment Examples 37 to 42.

The step 7 is a step of reacting a compound of the formula (20) with aborane compound of the general formula (16) or a diborane compound ofthe general formula (17) in the presence of a palladium catalyst and abase to give the compound of the formula (12) used in the step 6. Thisreaction can be effected with a high reaction yield of the targetcompound by adopting reaction conditions, which are described in TheJournal of Organic Chemistry, vol. 60, 7508-7510, 1995, or The Journalof Organic Chemistry, vol. 65, 164-168, 2000.

The palladium catalyst used in the step 7 includes, for example,palladium salts and complex compounds, which are exemplified with regardto the palladium catalyst used in the step 1. Of these catalysts,palladium complex compounds having a tertiary phosphine as a ligand arepreferable because of high reaction yield. Palladium complex compoundshaving a triphenylphosphine as a ligand are especially preferable inview of ease in availability and high reaction yield.

The amount of the palladium catalyst used in the step 7 is notparticularly limited, provided that it is a catalytical amount. Themolar ratio of the palladium catalyst to the compound of formula (20) ispreferably in the range of 1:50 to 1:10.

Palladium complex compounds having a tertiary phosphine as a ligand canalso be synthesized in a reaction system containing a palladium salt ora palladium complex compound and a tertiary phosphine added therein.

As specific examples of the tertiary phosphine used, those which areexemplified with regard to the step 1 can be mentioned. Of thesetertiary phosphines, triphenylphosphine is preferable in view of ease inavailability and high reaction yield.

The molar ratio of the tertiary phosphine to the palladium salt or thepalladium complex compound is preferably in the range of 1:10 to 10:1,and more preferably 1:2 to 5:1 because of high reaction yield.

It is essential to carry out the step 7 in the presence of a base. Thebase used in the step 7 includes, for example, sodium hydroxide,potassium hydroxide, sodium carbonate, potassium carbonate, lithiumcarbonate, cesium carbonate, potassium acetate, sodium acetate,potassium phosphate, sodium phosphate, sodium fluoride, potassiumfluoride and cesium fluoride. Of these, potassium acetate is preferablebecause of high reaction yield. The molar ratio of the base to thecompound of formula (20) is not particularly limited, but is preferablyin the range of 1:2 to 10:1, and more preferably 1:1 to 3:1 because ofhigh reaction yield.

The molar ratio of the borane compound of formula (16) or the diboranecompound of formula (17) to the compound of formula (20), which are usedin the step 2, is not particularly limited, but is preferably in therange of 1:1 to 5:1, and more preferably 2:1 to 3:1 because of highyield.

The reaction in the step 7 can be effected in a reaction medium. Thereaction medium used in the step 7 includes, for example, water,dimethylsulfoxide, dimethylformamide, tetrahydrofuran, 1,4-dixane,toluene, benzene, diethyl ether, ethanol, methanol and xylene. Thesereaction mediums may be used either alone or in combination. Of these,tetrahydrofuran and 1,4-dioxane are preferable because of high reactionyield.

The compound of formula (12) obtained in the step 7 may be isolatedafter completion of the reaction. Alternatively the compound of formula(12) may be used as a raw material in the step (6).

The cyclic azine compound of formula (1d) according to the presentinvention can be prepared, for example, by a process comprising a step 8involving the following reaction scheme.

In the reaction scheme of step 8, each Ar¹ represents an aromatic group,which is unsubstituted or substituted by an alkyl group having 1 to 4carbon atoms, a phenyl group or a pyridyl group. Each R¹ represents ahydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenylgroup; and groups R¹ in the two —B(OR¹)₂ groups may be the same ordifferent, and two groups R¹ in each of the two —B(OR¹)₂ groups may forma ring together with the oxygen atoms and the boron atom. Each Ar⁴represents an unsubstituted or substituted aromatic hydrocarbon groupcomprised of 2 to 4 rings. Y¹ represents a chlorine, bromine or iodineatom.

As preferable specific examples of the compound of formula (15), thosewhich have the following skeletals 15-1 through 15-5 are mentioned, butthe compound of formula (15) used in the present invention is notlimited thereto.

The step 8 is a step of reacting a compound of the formula (14) with acompound of the formula (15) in the presence of a palladium catalyst anda base to give the cyclic azine compound of formula (1d) according tothe present invention. This reaction can be effected with a highreaction yield of the target compound by reaction conditions, which areadopted in the conventional Suzuki-Miyaura reaction. The target compoundcan be obtained with a high yield by adopting such reaction conditions.

The palladium catalyst used in the step 8 includes, for example,palladium catalysts, which are exemplified with regard to the palladiumcatalysts used in the step 1. Palladium chloride, palladium acetate,tris(dibenzylideneacetone)dipalladium,dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium are preferable in view of ease in availability and goodreaction yield.

These palladium catalysts can also be synthesized in a reaction systemcontaining a palladium salt or a palladium complex compound and atertiary phosphine added therein.

As specific examples of the tertiary phosphine added to a palladium saltor a palladium complex compound, those which are mentioned with regardto the step 1 are mentioned. Of these, triphenylphosphine,tri(tert-butyl)phosphine, 2-di(tert-butylphosphino)biphenyl,2-dicylohexylphosphino-2′,4′,6′-triisopropylbiphenyl are preferable inview of ease in availability and good reaction yield.

The molar ratio of the palladium catalyst to the compound of formula (6)is preferably in the range of 1:200 to 1:2, and more preferably 1:100 to1:10 in view of good reaction yield.

The molar ratio of the tertiary phosphine to the palladium catalyst ispreferably in the range of 1/10 to 10/1, and more preferably 1/2 to 5/1in view of good reaction yield.

The base used in the step 8 includes, for example, those which areexemplified with regard to the step 1. Of these, sodium hydroxide isespecially preferable because of high reaction yield. The molar ratio ofthe base to the compound of formula (6) is preferably in the range of1:2 to 10:1, and more preferably 1:1 to 3:1 because of high reactionyield.

The molar ratio of the compound of formula (15) to the compound offormula (14), which are used in the step 8, is preferably in the rangeof 2:1 to 5:1, and more preferably 2:1 to 3:1 because of high yield.

The reaction medium used in the step 8 includes, for example, water,dimethylsulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene,diethyl ether and xylene. These reaction mediums may be used eitheralone or in combination. Of these, tetrahydrofuran is preferable becauseof high reaction yield.

The reaction in the step 8 can be effected at a temperatureappropriately chosen in a range of 0° C. to 150° C. A temperature of 50°C. to 80° C. is especially preferable because of high reaction yield.

The cyclic azine compound of formula (1d) of the present invention canbe obtained by conducting the conventional treating procedure aftercompletion of the step 8. If desired, the produced compound is purifiedby, for example, recrystallization, column chromatography orsublimation.

The compound of formula (14) used as a raw material for the preparationof the cyclic azine compound of formula (1d) of the present invention inthe step 8 can be synthesized by the process of the step (7).

The process for producing a thin film of the cyclic azine compound offormula (1) according to the present invention for an organic EL deviceis not particularly limited. For example, vacuum deposition, spincoating, ink-jetting, casting and dipping can be adopted for theformation of the thin film. The vacuum deposition can be conducted usinga conventional vacuum deposition apparatus. However, in consideration ofthe tact time and cost for the production of the organic EL device, thedegree of vacuum at the vacuum deposition is preferably in the range ofapproximately 1×10⁻² Pa to 1×10⁻⁵ Pa, which can be achieved, forexample, by the conventionally used diffusion pump, turbo-molecular pumpor cryopump. The rate of vacuum deposition varies depending upon thethickness of thin film, but the deposition rate is preferably in therange of 0.005 nm/sec to 1.0 nm/sec.

The solubility of the cyclic azine compound of formula (1) of thepresent invention in a solvent such as chloroform, dichloromethane,1,2-dichloroetane, chlorobenzene, toluene, ethyl acetate andtetrahydrofuran is high. Therefore, the thin film can also be formedfrom a solution thereof by, for example, spin coating, ink jetting,casting or dipping using the conventional apparatus.

EXAMPLES

The invention will now be described more specifically by the followingexperiment examples and test examples, but the scope of the invention isby no means limited thereto.

Experiment Example 1

In a stream of argon, 1.50 g (3.98 mmol) of2-(3,5-dichlorophenyl)-4,6-diphenylpyrimidine, 1.74 g (8.75 mmol) of4-(2-pyridyl)phenylboronic acid, 2.85 g (8.75 mmol) of cesium carbonate,36 mg (0.159 mmol) of palladium acetate and 152 mg (0.318 mmol) of2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were suspended in80 mL of 1,4-dioxane, and the obtained suspension was heated underreflux for 17 hours. The reaction mixture was cooled to roomtemperature, and was then distilled under a reduced pressure to removeall volatile materials. Methanol was added to the concentrate and thethus-deposited solid was collected by filtration. The thus-obtainedcrude product was purified by silica gel chromatography using chloroformas an eluent to give 2.19 g of the target2-[4,4″-di(2-pyridyl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-diphenylpyrimidineas a white solid (yield: 90%).

¹H-NMR (CDCl₃): δ7.19-7.23 (m, 2H), 7.53-7.50 (m, 6H), 7.70-7.79 (m,4H), 7.88 (d, J=8.5 Hz, 4H), 8.01-8.02 (m, 2H), 8.11 (d, J=8.3 Hz, 4H),8.25-8.29 (m, 4H), 8.68 (d, J=4.5 Hz, 2H), 8.95 (d, J=1.8 Hz, 2H).

¹³C-NMR (CDCl₃):δ110.7 (CH), 120.5 (CH×2), 122.2 (CH×2), 126.6 (CH×2),127.4 (CH×4), 127.5 (CH×4), 127.9 (CH×4), 128.2 (CH), 129.0 (CH×4),130.9 (CH×2), 136.8 (CH×2), 137.5 (quart.×2), 138.7 (quart.×2), 139.5(quart.), 141.6 (quart.), 141.8 (quart.), 149.9 (CH×2), 157.1 (quart.),164.4 (CH), 165.0 (CH×2).

Experiment Example 2

In a stream of argon, 1.59 g (3.43 mmol) of2-(3,5-dibromophenyl)-4,6-diphenylpyrimidine, 2.02 g (7.20 mmol) of2-[3-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]pyridine, 2.34g (7.20 mmol) of cesium carbonate, 31 mg (0.1372 mmol) of palladiumacetate and 131 mg (0.274 mmol) of2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were suspended in60 mL of tetrahydrofuran, and the obtained suspension was heated underreflux for 55 hours. The reaction mixture was cooled to roomtemperature, and was then distilled under a reduced pressure to removeall volatile materials. Methanol was added to the concentrate and thethus-deposited solid was collected by filtration. The thus-obtainedcrude product was purified by silica gel chromatography using ahexane/chloroform (1:1) mixed solvent as an eluent to give 1.69 g of thetarget2-[3,3″-di(2-pyridyl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-diphenylpyrimidineas a white solid (yield: 80%).

¹H-NMR (CDCl₃): δ7.17-7.23 (m, 2H), 7.49-7.61 (m, 8H), 7.68-7.83 (m,6H), 7.98 (t, J=0.9 Hz, 1H), 8.02 (s, 1H), 8.04 (t, J=1.8 Hz, 2H),8.24-8.28 (m, 4H), 8.33 (t, J=1.8 Hz, 2H), 8.65-8.68 (m, 2H), 8.93 (d,J=1.8 Hz, 2H).

¹³C-NMR (CDCl₃): δ111.0 (CH), 121.2 (CH×2), 122.7 (CH×2), 126.56 (CH×2),126.59 (CH×2), 127.0 (CH×2), 127.8 (CH×4), 128.7 (CH×2), 129.1 (CH),129.4 (CH×4), 129.7 (CH×2), 131.2 (CH×2), 137.2 (CH×2), 137.9(quart.×2), 140.0 (quart.), 140.4 (quart.×2), 142.3 (quart.×2), 142.5(quart.×2), 150.1 (CH×2), 157.8 (quart.×2), 164.9 (quart.), 165.3(quart.×2).

Experiment Example 3

In a stream of argon, 1.14 g (2.15 mmol) of4,6-bis(2-biphenylyl)-2-(3,5-dichlorophenyl)pyrimidine, 0.90 g (4.52mmol) of 4-(2-pyridyl)phenylboronic acid, 1.47 g (4.52 mmol) of cesiumcarbonate, 19 mg (0.086 mmol) of palladium acetate and 82 mg (0.172mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl weresuspended in 40 mL of tetrahydrofuran, and the obtained suspension washeated under reflux for 18 hours. The reaction mixture was cooled toroom temperature, and was then distilled under a reduced pressure toremove all volatile materials. The thus-deposited solid was collected byfiltration. The thus-obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:1) mixed solvent as aneluent to give 0.60 g of the target4,6-bis(2-biphenylyl)-2-[4,4″-di(2-pyridyl)-1,1′:3′,1″-terphenyl-5′-yl]pyrimidineas a white solid (yield: 37%).

¹H-NMR (CDCl₃): δ7.04 (s, 1H), 7.22-7.36 (m, 10H), 7.45-7.59 (m, 8H),7.80-7.89 (m, 8H), 7.96 (t, J=1.8 Hz, 1H), 8.18 (d, J=8.3 Hz, 4H), 8.25(d, J=1.8 Hz, 2H), 8.78 (bd, J=4.8 Hz, 2H).

Experiment Example 4

In a stream of argon, 0.50 g (1.32 mmol) of2-(3,5-dichlorophenyl)-4,6-di(2-pyridyl)pyrimidine, 0.55 g (2.76 mmol)of 4-(2-pyridyl)phenylboronic acid, 0.90 g (2.77 mmol) of cesiumcarbonate, 24 mg (0.106 mmol) of palladium acetate and 101 mg (0.211mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl weresuspended in 30 mL of tetrahydrofuran, and the obtained suspension washeated under reflux for 17 hours. The reaction mixture was cooled toroom temperature, and was then distilled under a reduced pressure toremove all volatile materials. Methanol was added to the concentrate andthe thus-deposited solid was collected by filtration. The thus-obtainedcrude product was purified by silica gel chromatography using chloroformas an eluent to give 0.46 g of the target2-[4,4″-di(2-pyridyl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-di(2-pyridyl)pyrimidineas a white solid (yield: 56%).

¹H-NMR (CDCl₃): δ7.17-7.26 (m, 2H), 7.40 (ddd, J=7.5, 4.8, 1.0 Hz, 2H),7.69-7.78 (m, 4H), 7.83-7.89 (m, 6H), 8.00 (t, J=1.6 Hz, 1H), 8.12 (d,J=8.3 Hz, 4H), 8.67-8.70 (m, 4H), 8.74 (d, J=4.0 Hz, 2H), 8.94 (d, J=1.8Hz, 2H), 9.31 (s, 1H).

¹³C-NMR (CDCl₃): δ112.0 (CH), 120.6 (CH×2, CH×2), 122.0 (CH×2), 122.3(CH×2), 125.4 (CH×2), 126.5 (CH×4), 127.5 (CH×4), 127.9 (CH), 136.9(CH×2), 137.1 (CH×2), 138.7 (quart.×2), 139.2 (quart.), 141.7(quart.×2), 141.8 (quart.×2), 149.7 (CH×2), 149.8 (CH×2), 154.7(quart.×2), 157.1 (quart.×2), 163.9 (quart.), 164.5 (quart.×2).

Experiment Example 5

In a stream of argon, 0.40 g (0.81 mmol) of2-(3,5-dibromophenyl)-4,6-di-p-tolylpyrimidine, 0.48 g (1.70 mmol) of4-[4-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-pyridine, 0.55g (1.70 mmol) of cesium carbonate, 7 mg (0.032 mmol) of palladiumacetate and 31 mg (0.065 mmol) of2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were suspended in20 mL of tetrahydrofuran, and the obtained suspension was heated underreflux for 87 hours. The reaction mixture was cooled to roomtemperature, and was then distilled under a reduced pressure to removeall volatile materials. Methanol was added to the concentrate and thethus-deposited solid was collected by filtration. The thus-obtainedcrude product was purified by silica gel chromatography using achloroform/methanol (100:1) mixed solvent as an eluent to give 0.30 g ofthe target2-[4,4″-di(4-pyridyl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-di-p-tolylpyrimidineas a white solid (yield: 58%).

¹H-NMR (CDCl₃): δ2.50 (s, 6H), 7.41 (d, J=8.0 Hz, 4H), 7.63 (dd, J=4.5,1.5 Hz, 4H), 7.84 (d, J=8.3 Hz, 4H), 7.95 (d, J=8.3 Hz, 4H), 8.03 (t,J=1.8 Hz, 1H), 8.05 (s, 1H), 8.24 (d, J=8.0 Hz, 4H), 8.73 (dd, J=4.5,1.5 Hz, 4H), 9.02 (d, J=1.8 Hz, 2H).

¹³C-NMR (CDCl₃): δ21.6 (CH3), 31.0 (CH3), 110.1 (CH), 121.5 (CH×4),126.7 (CH×2), 127.3 (CH×4), 127.5 (CH×4), 128.2 (CH×4), 129.7 (CH×4),134.7 (quart.×2), 137.3 (quart.×2), 139.9 (quart.), 141.2 (quart.×2),141.3 (quart.×2), 142.0 (quart.×2), 147.9 (quart.×2), 150.4 (CH×4),164.0 (quart.), 164.7 (quart.×2).

Experiment Example 6

In a stream of argon, 0.50 g (0.88 mmol) of2-(3,5-dibromophenyl)-4,6-di(2-naphthyl)pyrimidine, 0.95 g (2.82 mmol)of2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)-phenyl]-1,10-phenanthroline,0.63 g (1.94 mmol) of cesium carbonate, 8 mg (0.035 mmol) of palladiumacetate and 34 mg (0.070 mmol) of2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were suspended in40 mL of toluene, and the obtained suspension was heated under refluxfor 14 hours. The reaction mixture was cooled to room temperature, andwas then distilled under a reduced pressure to remove all volatilematerials. Methanol was added to the concentrate and the thus-depositedsolid was collected by filtration. The thus-obtained crude product waspurified by silica gel chromatography using chloroform as an eluent togive 0.25 g of the target2-[4,4″-bis(1,10-phenanthrorin-2-yl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-di(2-naphthyl)pyrimidineas a yellow solid (yield: 31%).

¹H-NMR (CDCl₃): δ7.52-7.55 (m, 4H), 7.61 (dd, J=4.4, 0.3 Hz, 2H),7.73-7.82 (m, 4H), 7.88-7.92 (m, 2H), 8.00-8.09 (m, 8H), 8.13 (bs, 1H),8.12-8.24 (m, 4H), 8.31 (d, J=8.5 Hz, 2H), 8.34 (s, 1H), 8.46 (d, J=8.3Hz, 2H), 8.53 (d, J=8.0 Hz, 4H), 8.85 (bs, 2H), 9.10 (bs, 2H), 9.23 (d,J=4.3 Hz, 2H).

Experiment Example 7

In a stream of argon, 0.18 g (0.32 mmol) of2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-4,6-diphenylpyrimidine,0.19 g (0.82 mmol) of 3-(4-bromophenyl)-pyridine, 0.25 g (0.76 mmol) ofcesium carbonate and 23 mg (0.033 mmol) ofdichlorobis(triphenylphosphine) palladium were suspended in 10 mL oftetrahydrofuran, and the obtained suspension was heated under reflux for12 hours. The reaction mixture was cooled to room temperature, and wasthen distilled under a reduced pressure to remove all volatilematerials. Methanol was added to the concentrate and the thus-depositedsolid was collected by filtration. The thus-obtained crude product waspurified by silica gel chromatography using a hexane/chloroform (1:1)mixed solvent as an eluent to give 77 mg of the target2-[4,4″-di(3-pyridyl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-diphenylpyrimidineas a white solid (yield: 39%).

¹H-NMR (CDCl₃): δ7.30-7.35 (m, 2H), 7.39-7.50 (m, 6H), 7.67 (d, J=7.8Hz, 4H), 7.84 (d, J=7.8 Hz, 4H), 7.86-7.93 (m, 2H), 7.98 (s, 1H),8.22-8.24 (m, 5H), 8.55 (d, J=4.3 Hz, 2H), 8.88 (bs, 2H), 8.91 (bs, 2H).

Experiment Example 8

In a stream of argon, 0.40 g (0.75 mmol) of2-(3,5-dibromophenyl)-4-(2-naphthyl)-6-p-tolylpyrimidine, 0.47 g (1.66mmol) of5-[4-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]pyrimidine,0.54 g (1.66 mmol) of cesium carbonate, 7 mg (0.030 mmol) of palladiumacetate and 29 mg (0.060 mmol) of2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were suspended in15 mL of tetrahydrofuran, and the obtained suspension was heated underreflux for 15 hours. The reaction mixture was cooled to roamtemperature, and was then distilled under a reduced pressure to removeall volatile materials. Methanol was added to the concentrate and thethus-deposited solid was collected by filtration. The thus-obtainedcrude product was purified by silica gel chromatography using ahexane/chloroform (1:1) mixed solvent as an eluent to give 0.28 mg ofthe target 2-[4,4″-di(5-pyrimidyl)-,1′:3′,1″-terphenyl-5′-yl]-4-(2-naphthyl)-6-p-tolylpyrimidine as ayellowish white solid (yield: 54%).

¹H-NMR (CDCl₃): δ2.40 (s, 3H), 7.32 (d, J=8.0 Hz, 2H), 7.46-7.54 (m,2H), 7.68 (d, J=8.3 Hz, 4H), 7.83-7.97 (m, 8H), 8.08 (s, 1H), 8.17 (d,J=8.0 Hz, 2H), 8.33 (dd, J=8.8, 0.1 Hz, 1H), 8.68 (bs, 1H), 8.94 (d,J=1.5 Hz, 2H), 8.98 (bs, 4H), 9.12 (bs, 2H).

¹³C-NMR (CDCl₃): δ21.5 (CH3), 110.7 (CH), 124.3 (CH), 126.7 (CH), 126.8(CH), 127.3 (CH×2, CH×2), 127.5 (CH×4), 127.9 (CH), 128.0 (CH), 128.5(CH×4), 128.8 (CH), 129.1 (CH), 129.8 (CH×2), 133.3 (quart.), 133.5(quart.×2), 134.0 (quart.×2), 134.6 (quart.), 134.7 (quart.), 134.9(quart.), 139.9 (quart.), 141.1 (quart.×2), 141.5 (quart.), 141.9(quart.×2), 154.9 (CH×4) 157.7 (CH), 164.1 (quart.), 154.8 (quart.),164.9 (quart.).

Experiment Example 9

In a stream of argon, 0.15 g (0.26 mmol) of2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-4,6-diphenylpyrimidineand 0.19 g (0.66 mmol) of 2-(4-bromophenyl)-1,3-benzothiazol, 77 mg(0.066 mmol) of tetrakis(triphenylphosphine) palladium were suspended ina mixture of 3 mL of an aqueous 2M sodium carbonate solution and 6 mL oftoluene, and the obtained suspension was heated under reflux for 24hours. The reaction mixture was cooled to room temperature, and was thendistilled under a reduced pressure to remove all volatile materials.Methanol was added to the concentrate and the thus-deposited solid wascollected by filtration. The thus-obtained crude product was purified bysilica gel chromatography using a chloroform/methanol (100:1) mixedsolvent as an eluent to give 0.12 g of the target2-[4,4″-di(2-benzothiazolyl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-diphenylpyrimidineas a white solid (yield: 65%).

¹H-NMR (CDCl₃): δ7.30-7.36 (m, 2H), 7.42-7.56 (m, 8H), 7.78-7.87 (m,6H), 7.95-7.97 (m, 1H), 7.99 (s, 1H), 8.04 (d, J=7.8 Hz, 2H), 8.18 (d,J=8.3 Hz, 4H), 8.22-8.26 (m, 4H), 8.94 (d, J=1.8 Hz, 2H).

Experiment Example 10

In a stream of argon, 0.34 g (1.62 mmol) of 6-bromoquinoline wasdissolved in 7 mL of tetrahydrofuran, and then 1.03 mL of a solution ofbutyllithium 1.63 mmol in hexane was added dropwise at −78° C. Theresultant mixture was stirred at −78° C. for 30 minutes, and then 0.41 g(1.63 mmol) of dichloro(tetramethylethylenediamine) zinc was added. Themixture was heated to room temperature and maintained at thattemperature for 1 hour while being stirred. To the resultant mixture,0.20 g (0.41 mmol) of 2-(3,5-dibromophenyl)-4,6-di-p-tolylpyrimidine, 19mg (0.016 mmol) of tetrakis(triphenylphosphine)palladium and 3 mL oftetrahydrofuran were added, and the obtained suspension was heated underreflux for 17 hours. The reaction mixture was cooled to roomtemperature, and was then distilled under a reduced pressure to removeall volatile materials. The thus-deposited solid was collected byfiltration. The thus-obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:1) mixed solvent as aneluent to give 0.16 g of the target2-[3,5-di(6-quinolyl)phenyl-4,6-di-p-tolylpyrimidine as a white solid(yield: 65%).

¹H-NMR (CDCl₃): δ2.49 (s, 6H), 7.33-7.38 (m, 2H), 7.41 (d, J=8.0 Hz,4H), 8.03 (t, J=1.8 Hz, 1H), 8.05 (s, 1H), 8.09-8.34 (m, 8H), 8.24 (d,J=8.0 Hz, 4H), 8.92 (dd, J=4.3, 1.5 Hz, 2H), 9.02 (d, J=1.8 Hz, 2H).

Experiment Example 11

In a stream of argon, 0.45 g (0.85 mmol) of2-(3,5-dichlorophenyl)-4,6-bis[4-(3-pyridyl)phenyl]pyrimidine, 0.37 g(1.87 mmol) of m-biphenylboronic acid, 0.39 g (1.86 mmol) of potassiumphosphate, 8 mg (0.034 mmol) of palladium acetate and 32 mg (0.068 mmol)of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were suspendedin 20 mL of tetrahydrofuran, and the obtained suspension was heatedunder reflux for 66 hours. The reaction mixture was cooled to roomtemperature, and was then distilled under a reduced pressure to removeall volatile materials. Methanol was added to the concentrate, and thethus-deposited solid was collected by filtration. The thus-obtainedcrude product was purified by silica gel chromatography using chloroformas an eluent to give 0.42 g of the target4,6-bis[4-(3-pyridyl)phenyl]-2-(1,1′:3′,1″:3″,1″:3″,1″″-quinquephenyl-5″-yl)pyrimidineas a white solid (yield: 64%).

¹H-NMR (CDCl₃): δ7.28-7.44 (m, 8H), 7.51-7.66 (m, 8H), 7.71-7.75 (m,6H), 7.89 (t, J=1.9 Hz, 2H), 7.91-7.94 (m, 2H), 7.98 (t, J=1.6 Hz, 1H),8.08 (s, 1H), 8.38 (d, J=8.3 Hz, 4H), 8.58 (dd, J=4.8, 1.5 Hz, 2H), 8.88(d, J=2.3 Hz, 2H), 8.93 (d, J=1.8 Hz, 2H).

Experiment Example 12

In a stream of argon, 5.00 g (10.7 mmol) of2-(3,5-dibromophenyl)-4,6-diphenylpyrimidine, 3.70 g (23.6 mmol) of3-chlorophenylboronic acid, 7.69 g (23.6 mmol) of cesium carbonate and300 mg (0.43 mmol) of dichlorobis(triphenylphosphine)palladium weresuspended in 100 mL of tetrahydrofuran, and the obtained suspension washeated under reflux for 15 hours. The reaction mixture was cooled toroom temperature, and was then distilled under a reduced pressure toremove all volatile materials. The thus-deposited solid was collected byfiltration. The thus-obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:1) mixed solvent as aneluent to give 3.58 g of the target2-(3,3″-dichloro-(1,1′:3′,1″-terphenyl-5′-yl)-4,6-diphenylpyrimidine asa white solid (yield: 63%).

¹H-NMR (CDCl₃): δ7.32-7.43 (m, 4H), 7.51-7.55 (m, 6H), 7.60 (dt, J=7.3,1.5 Hz, 2H), 7.69 (t, J=1.5 Hz, 2H), 7.79 (t, J=1.8 Hz, 1H), 8.01 (s,1H), 8.22-8.26 (m, 4H), 8.84 (d, J=1.8 Hz, 2H).

Experiment Example 13

In a stream of argon, 0.50 g (0.94 mmol) of2-(3,3″-dichloro-(1,1′:3′,1″-terphenyl-5′-yl)-4,6-diphenylpyrimidine,0.67 g (4.16 mmol) of benzofurylboronic acid, 1.35 g (4.16 mmol) ofcesium carbonate, 8 mg (0.038 mmol) of palladium acetate and 36 mg(0.075 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenylwere suspended in 20 mL of 1,4-dioxane, and the obtained suspension washeated under reflux for 14 hours. The reaction mixture was cooled toroom temperature, and was then distilled under a reduced pressure toremove all volatile materials. Methanol was added to the concentrate,and the thus-deposited solid was collected by filtration. Thethus-obtained crude product was purified by silica gel chromatographyusing a hexane/chloroform (1/1) mixed solvent as an eluent to give 0.16g of the target2-[3,3″-di(2-benzofuryl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-diphenylpyrimidineas a white solid (yield: 25%).

¹H-NMR (CDCl₃): δ7.09 (s, 2H), 7.15-7.27 (m, 4H), 7.48-7.59 (m, 12H),7.74 (bd, J=7.7 Hz, 2H), 7.87 (bd, J=7.8 Hz, 2H), 8.01 (t, J=1.8 Hz,1H), 8.03 (s, 1H), 8.23-8.30 (m, 6H), 8.96 (d, J=1.8 Hz, 2H).

¹³C-NMR (CDCl₃): δ101.9 (CH×2), 110.8 (CH), 111.3 (CH×2), 121.0 (CH×2),123.0 (CH×2), 124.1 (CH×2), 124.2 (CH×2), 124.5 (CH×2), 126.8 (CH×2),127.4 (CH×4), 127.9 (CH×2), 128.6 (CH), 129.1 (CH×4), 129.3 (quart.×2),129.4 (CH×2), 131.0 (CH×2), 131.2 (quart.×2), 137.5 (quart.×2), 139.6(quart.), 141.9 (quart.×2), 142.0 (quart.×2), 155.1 (quart.×2), 155.9(quart.×2), 164.4 (quart.), 165.0 (quart.×2).

Experiment Example 14

In a stream of argon, 1.00 g (2.15 mmol) of2-(3,5-dibramophenyl)-4,6-diphenylpyrimidine, 1.20 g (4.73 mmol) ofbispinacolatediborane, 0.70 g (7.09 mmol) of potassium acetate and 91 mg(0.129 mmol) of dichlorobis(triphenylphosphine)palladium were suspendedin 20 mL of tetrahydrofuran, and the obtained suspension was heatedunder reflux for 77 hours. The reaction mixture was cooled to roomtemperature, and was then distilled under a reduced pressure to removeall volatile materials. The thus-deposited solid was collected byfiltration. The obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:1) mixed solvent as aneluent to give 0.68 g of the target2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-4,6-diphenylpyrimidineas a white solid (yield: 56%).

¹H-NMR (CDCl₃): δ1.32 (s, 24H), 7.49-7.52 (m, 6H), 7.94 (s, 1H),8.23-8.27 (m, 4H), 8.34 (bs, 1H), 9.09 (d, J=1.3 Hz, 2H).

Experiment Example 15

In a stream of argon, 1.91 g (8.56 mmol) of 9-phenanthreneboronic acid,4.00 g (8.56 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazineand 98.9 mg (0.086 mmol) of tetrakis(triphenylphosphine) palladium weresuspended in a mixed solvent composed of 320 mL of toluene and 40 mL ofethanol, and the resultant suspension was heated to 60° C. To thesuspension, 25.7 mL (25.7 mmol) of an aqueous 1M K₂CO₃ solution wasgradually added dropwise, and the mixture was stirred for 4 hours. Thenthe mixture was cooled to room temperature, and 2.56 g (12.8 mmol) of4-(2-pyridyl)phenylboronic acid and 25.7 mL (25.7 mmol) of an aqueous 1MK₂CO₃ solution were added. Then the mixture was heated to 70° C. andmaintained at that temperature for 12 hours while being stirred. Thenthe reaction mixture was cooled to room temperature, and was thendistilled under a reduced pressure to remove all volatile materials.Methanol was added to the concentrate, and the thus-deposited solid wascollected by filtration. The obtained crude product was purified bysilica gel chromatography using a hexane/chloroform (1:2) mixed solventas an eluent to give 3.91 g of the target4,6-diphenyl-2-[5-(9-phenanthryl)-4′-(2-pyridyl)biphenyl-3-yl]-1,3,5-triazineas a white solid (yield: 64%).

¹H-NMR (CDCl₃): δ.7.31 (d, J=7.00 Hz, 1H), 7.58-7.65 (m, 8H), 7.70 (t,J=7.0 Hz, 1H), 7.76 (t, J=7.0 Hz, 2H), 7.82-7.87 (m, 2H), 7.93 (s, 1H),7.99 (d, J=8.5 Hz, 2H), 8.02 (d, J=8.2 Hz, 1H), 8.06 (d, J=8.0 Hz, 1H),8.12 (s, 1H), 8.23 (d, J=8.4 Hz, 2H), 8.78 (d, J=8.2 Hz, 1H), 8.82 (d,J=8.1 Hz, 4H), 8.89 (d, J=8.2 Hz, 1H), 8.98 (s, 1H), 9.21 (s, 1H).

The obtained triazine compound exhibited a Tg of 133° C.

Experiment Example 16

In a stream of argon, 0.98 g (3.21 mmol) of9-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)anthracene, 1.50 g (3.21mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine and 37.1 mg(0.032 mmol) of tetrakis(triphenylphosphine)palladium were suspended ina mixed solvent composed of 100 mL of toluene and 20 mL of ethanol, andthe resultant suspension was heated to 60° C. To the suspension, 9.63 mL(9.63 mmol) of an aqueous 1M K₂CO₃ solution was gradually addeddropwise, and the mixture was stirred for 3 hours. Then the mixture wascooled to room temperature, and 0.96 g (4.82 mmol) of4-(2-pyridyl)phenylboronic acid and 6.42 mL (6.42 mmol) of an aqueous 1MK₂CO₃ solution were added. Then the mixture was heated to 60° C. andmaintained at that temperature for 17 hours while being stirred.

Then the reaction mixture was cooled to room temperature, and was thendistilled under a reduced pressure to remove all volatile materials.Methanol was added to the concentrate, and the thus-deposited solid wascollected by filtration. The obtained crude product was purified bysilica gel chromatography using a hexane/chloroform (1:2) mixed solventas an eluent to give 0.68 g of the target2-[5-(9-anthryl)-4′-(2-pyridyl)biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazineas a white solid (yield: 33%).

¹H-NMR (CDCl₃): δ.7.34 (brs, 1H), 7.44 (t, J=7.6 Hz, 2H), 7.53-7.64 (m,9H), 7.85-7.88 (m, 4H), 8.01 (d, J=7.6 Hz, 2H), 8.03 (s, 1H), 8.16 (d,J=8.5 Hz, 2H) 8.23 (d, J=8.3 Hz, 2H), 8.64 (s, 1H), 8.79 (d, J=5.6 Hz,4H), 8.89 (s, 1H), 9.31 (s, 1H).

Experiment Example 17

In a stream of argon, 0.37 g (2.14 mmol) of 1-naphthaleneboronic acid,1.00 g (2.14 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazineand 24.7 mg (0.021 mmol) of tetrakis(triphenylphosphine)palladium weresuspended in a mixed solvent composed of 80 mL of toluene and 10 mL ofethanol, and the resultant suspension was heated to 60° C. To thesuspension, 8.56 mL (8.56 mmol) of an aqueous 1M K₂CO₃ solution wasgradually added dropwise, and the mixture was stirred for 3 hours. Thenthe mixture was cooled to room temperature, and 0.64 g (3.21 mmol) of4-(2-pyridyl)phenylboronic acid wad added. Then the mixture was heatedto 70° C. and maintained at that temperature for 3 hours while beingstirred. Then the reaction mixture was cooled to room temperature, andwas then distilled under a reduced pressure to remove all volatilematerials. Methanol was added to the concentrate, and the thus-depositedsolid was collected by filtration. The obtained crude product waspurified by silica gel chromatography using a hexane/chloroform (1:2)mixed solvent as an eluent to give 0.61 g of the target4,6-diphenyl-2-[5-(1-naphthyl)-4′-(2-pyridyl)biphenyl-3-yl]-1,3,5-triazineas a white solid (yield: 49%).

¹H-NMR (CDCl₃): δ.7.32 (t, J=6.5 Hz, 1H), 7.53 (t, J=6.9 Hz, 1H),7.57-7.68 (m, 10H), 7.83-7.87 (m, 2H), 7.98 (d, J=8.4 Hz, 2H), 8.00-8.05(m, 2H), 8.07 (s, 1H), 8.23 (d, J=6.7 Hz, 2H), 7.79 (d, J=6.5 Hz, 1H),8.82 (d, J=8.5 Hz, 4H), 8.93 (s, 1H), 9.18 (s, 1H).

The obtained triazine compound exhibited a Tg of 107° C.

Experiment Example 18

In a stream of argon, 0.53 g (2.14 mmol) of 1-pyreneboronic acid, 1.00 g(2.14 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine and24.7 mg (0.0214 mmol) of tetrakis(triphenylphosphine)palladium weresuspended in a mixed solvent composed of 80 mL of toluene and 10 mL ofethanol, and the resultant suspension was heated to 60° C. To thesuspension, 8.56 mL (8.56 mmol) of an aqueous 1M K₂CO₃ solution wasgradually added dropwise, and the mixture was stirred for 3 hours. Thenthe mixture was cooled to room temperature, and 0.64 g (3.21 mmol) of4-(2-pyridyl)phenylboronic acid wad added. Then the mixture was heatedto 70° C. and maintained at that temperature for 3 hours while beingstirred. Then the reaction mixture was cooled to room temperature, andwas then distilled under a reduced pressure to remove all volatilematerials. Methanol was added to the concentrate, and the thus-depositedsolid was collected by filtration. The obtained crude product waspurified by silica gel chromatography using a hexane/chloroform (1:2)mixed solvent as an eluent to give 0.37 g of the target4,6-diphenyl-2-[5-(1-pyrenyl)-4′-(2-pyridyl)biphenyl-3-yl]-1,3,5-triazineas a white solid (yield: 26%).

¹H-NMR (CDCl₃): δ.7.35 (brs, 1H), 7.57-7.65 (m, 6H), 7.86-7.91 (m, 2H),8.03 (d, J=8.4 Hz, 2H), 8.08 (t, J=7.6 Hz, 1H), 8.13 (d, J=9.3 Hz, 1H),8.18-8.29 (m, 8H), 8.33 (d, J=9.3 Hz, 1H), 8.37 (d, J=7.8 Hz, 1H), 8.80(d, J=4.8 Hz, 1H), 8.83 (d, J=7.9 Hz, 4H), 9.07 (s, 1H), 9.23 (s, 1H).

Experiment Example 19

In a stream of argon, 0.54 g (2.42 mmol) of 9-phenanthreneboronic acid,1.50 g (2.42 mmol) of4,6-bis(biphenyl-3-yl)-2-(3,5-dibromophenyl)-1,3,5-triazine and 56.0 mg(0.048 mmol) of tetrakis(triphenylphosphine)palladium were suspended ina mixed solvent composed of 150 mL of toluene and 20 mL of ethanol, andthe resultant suspension was heated to 60° C. To the suspension, 7.26 mL(7.26 mmol) of an aqueous 1M K₂CO₃ solution was gradually addeddropwise, and the mixture was stirred for 3 hours. Then the mixture wascooled to room temperature, and 0.72 g (3.63 mmol) of4-(2-pyridyl)phenylboronic acid and 7.26 mL (7.26 mmol) of an aqueous 1MK₂CO₃ solution were added. Then the mixture was heated to 60° C. andmaintained at that temperature for 4 hours while being stirred. Then thereaction mixture was cooled to room temperature, and was then distilledunder a reduced pressure to remove all volatile materials. Methanol wasadded to the concentrate, and the thus-deposited solid was collected byfiltration. The obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:2) mixed solvent as aneluent to give 1.1 g of the target4,6-bis(biphenyl-3-yl)-2-[5-(9-phenanthryl)-4′-(2-pyridyl)biphenyl-3-yl]-1,3,5-triazine as a white solid (yield: 58%).

¹H-NMR (CDCl₃): δ.7.34 (brs, 1H), 7.43 (t, J=7.4 Hz, 2H), 7.52 (t, J=7.4Hz, 4H), 7.66 (t, J=8.1 Hz, 1H), 7.68 (t, J=7.7 Hz, 2H), 7.70 (t, J=7.7Hz, 1H), 7.74-7.78 (m, 2H), 7.76 (d, J=8.4 Hz, 4H), 7.87 (d, J=7.6 Hz,4H), 7.94 (s, 1H), 8.00 (d, J=8.4 Hz, 2H), 8.01 (d, J=7.7 Hz, 1H), 8.12(t, J=7.4 Hz, 1H), 8.14 (s, 1H), 8.23 (d, J=8.3 Hz, 2H), 8.80 (d, J=7.8Hz, 1H), 8.80 (d, J=7.8 Hz, 2H), 8.82 (d, J=8.3 Hz, 1H), 8.88 (d, J=8.3Hz, 1H), 9.01 (s, 1H), 9.05 (s, 2H), 9.21 (s, 1H).

The obtained triazine compound exhibited a Tg of 119° C.

Experiment Example 20

In a stream of argon, 0.71 g (3.21 mmol) of 9-phenanthreneboronic acid,1.50 g (3.21 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazineand 37.0 mg (0.0321 mmol) of tetrakis(triphenylphosphine)palladium weresuspended in a mixed solvent composed of 120 mL of toluene and 15 mL ofethanol, and the resultant suspension was heated to 60° C. To thesuspension, 9.63 mL (9.63 mmol) of an aqueous 1M K₂CO₃ solution wasgradually added dropwise, and the mixture was stirred for 6 hours. Thenthe mixture was cooled to room temperature, and 0.59 g (4.82 mmol) of3-pyridineboronic acid and 9.63 mL (9.63 mmol) of an aqueous 1M K₂CO₃solution were added. Then the mixture was heated to 60° C. andmaintained at that temperature for 18 hours while being stirred. Thenthe reaction mixture was cooled to room temperature, and was thendistilled under a reduced pressure to remove all volatile materials.Methanol was added to the concentrate, and the thus-deposited solid wascollected by filtration. The obtained crude product was purified bysilica gel chromatography using a hexane/chloroform (1:2) mixed solventas an eluent to give 0.87 g of the target4,6-diphenyl-2-[5-(9-phenanthryl)-3-(3-pyridyl)phenyl]-1,3,5-triazine asa white solid (yield: 48%).

¹H-NMR (CDCl₃): δ.7.59-7.67 (m, 8H), 7.72 (t, J=7.0 Hz, 1H), 7.76-7.80(m, 2H), 7.90 (s, 1H), 7.90 (brt, J=6.5 Hz, 1H), 7.96 (d, J=8.1 Hz, 1H),8.02 (d, J=7.1 Hz, 1H), 8.05 (s, 1H), 8.60 (d, J=8.0 Hz, 1H), 8.80 (d,J=7.0 Hz, 4H), 8.83 (d, J=8.4 Hz, 1H), 8.89 (d, J=8.3 Hz, 1H), 9.13 (d,J=5.4 Hz, 1H), 9.14 (s, 1H), 9.22 (s, 1H).

Experiment Example 21

In a stream of argon, 0.71 g (3.21 mmol) of 9-phenanthreneboronic acid,1.50 g (3.21 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazineand 37.0 mg (0.0321 mmol) of tetrakis(triphenylphosphine)palladium weresuspended in a mixed solvent composed of 120 mL of toluene and 15 mL ofethanol, and the resultant suspension was heated to 60° C. To thesuspension, 9.63 mL (9.63 mmol) of an aqueous 1M K₂CO₃ solution wasgradually added dropwise, and the mixture was stirred for 8 hours.

Then the mixture was cooled to room temperature, and 0.59 g (4.82 mmol)of 3-(3-pyridyl)phenylboronic acid and 9.63 mL (9.63 mmol) of an aqueous1M K₂CO₃ solution were added. Then the mixture was heated to 60° C. andmaintained at that temperature for 18 hours while being stirred. Thenthe reaction mixture was cooled to room temperature, and was thendistilled under a reduced pressure to remove all volatile materials.Methanol was added to the concentrate, and the thus-deposited solid wascollected by filtration. The obtained crude product was purified bysilica gel chromatography using a hexane/chloroform (1:2) mixed solventas an eluent to give 0.86 g of the target4,6-diphenyl-2-[5-(9-phenanthryl)-3′-(3-pyridyl)biphenyl-3-yl]-1,3,5-triazineas a white solid (yield: 42%).

¹H-NMR (CDCl₃): δ.7.57-7.66 (m, 7H), 7.69-7.72 (m, 2H), 7.44-7.81 (m,3H), 7.81 (dd, J=8.0, 5.4 Hz, 1H), 7.92 (s, 1H), 8.02 (t, J=7.80 Hz,4H), 8.07 (s, 1H), 8.46 (d, J=8.1 Hz, 1H), 8.72 (d, J=5.3 Hz, 1H), 8.81(d, J=7.0 Hz, 4H), 8.82 (d, J=8.2 Hz, 1H), 8.88 (d, J=8.2 Hz, 1H), 9.02(s, 1H), 9.06 (s, 1H), 9.14 (s, 1H).

The obtained triazine derivative exhibited a Tg of 112° C.

Experiment Example 22

In a stream of argon, 0.43 g (1.93 mmol) of 9-phenanthreneboronic acid,0.90 g (1.93 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazineand 22.3 mg (0.0193 mmol) of tetrakis-(triphenylphosphine)palladium weresuspended in a mixed solvent composed of 75 mL of toluene and 10 mL ofethanol, and the resultant suspension was heated to 60° C. To thesuspension, 5.78 mL (5.78 mmol) of an aqueous 1M K₂CO₃ solution wasgradually added dropwise, and the mixture was stirred for 7 hours.

Then the mixture was cooled to room temperature, and 0.57 g (2.89 mmol)of 3-(6-phenyl)pyridineboronic acid and 5.78 mL (5.78 mmol) of anaqueous 1M K₂CO₃ solution were added. Then the mixture was heated to 70°C. and maintained at that temperature for 14 hours while being stirred.Then the reaction mixture was cooled to room temperature, and was thendistilled under a reduced pressure to remove all volatile materials.Methanol was added to the concentrate, and the thus-deposited solid wascollected by filtration. The obtained crude product was purified bysilica gel chromatography using a hexane/chloroform (1:2) mixed solventas an eluent to give 0.73 g of the target4,6-diphenyl-2-[5-(9-phenanthryl)-1-(6-phenylpyridin-3-yl)phenyl-3-yl]-1,3,5-triazineas a white solid (yield: 59%).

¹H-NMR (CDCl₃): δ.7.50 (t, J=6.8 Hz, 1H), 7.55-7.66 (m, 9H), 7.71 (t,J=6.8 Hz, 1H), 7.77 (t, J=7.0 Hz, 2H), 7.93 (s, 1H), 7.95 (d, J=8.2 Hz,1H), 8.02 (d, J=7.8 Hz, 1H), 8.05 (d, J=8.3 Hz, 1H), 8.10 (s, 1H), 8.14(d, J=7.2 Hz, 2H), 8.24 (d, J=7.0 Hz, 1H), 8.82 (d, J=6.9 Hz, 4H), 8.85(d, J=8.2 Hz, 1H), 8.89 (d, J=8.2 Hz, 1H), 9.03 (s, 1H), 9.22 (s, 1H),9.26 (s, 1H).

The obtained triazine derivative exhibited a Tg of 127° C.

Experiment Example 23

In a stream of argon, 0.714 g (3.22 mmol) of 9-phenanthreneboronic acid,1.50 g (3.22 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenylpyrimidine and37.2 mg (0.0322 mmol) of tetrakis(triphenylphosphine)palladium weresuspended in a mixed solvent composed of 120 mL of toluene and 15 mL ofethanol, and the resultant suspension was heated to 50° C. To thesuspension, 9.66 mL (9.66 mmol) of an aqueous 1M K₂CO₃ solution wasgradually added dropwise, and the mixture was stirred for 18 hours. Thenthe mixture was cooled to room temperature, and 0.961 g (4.83 mmol) of4-(2-pyridyl)phenylboronic acid and 9.66 mL (9.66 mmol) of an aqueous 1MK₂CO₃ solution were added. Then the mixture was heated to 60° C. andmaintained at that temperature for 4 hours while being stirred. Then thereaction mixture was cooled to room temperature, and was then distilledunder a reduced pressure to remove all volatile materials. Methanol wasadded to the concentrate, and the thus-deposited solid was collected byfiltration. The obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:2) mixed solvent as aneluent to give 1.28 g of the target4,6-diphenyl-2-[5-(9-phenanthryl)-4′-(2-pyridyl)biphenyl-3-yl]-pyrimidineas a white solid (yield: 62%).

¹H-NMR (CDCl₃): δ. 7.25 (t, J=4.9 Hz, 1H), 7.53-7.58 (m, 6H), 7.60 (d,J=7.5 Hz, 1H), 7.66 (t, J=7.0 Hz, 1H), 7.12 (t, J=8.2 Hz, 2H), 7.62-7.83(m, 2H), 7.90 (s, 1H), 7.95-8.00 (m, 4H), 8.07 (d, J=8.1 Hz, 1H), 8.09(s, 1H), 8.17 (d, J=8.5 Hz, 1H), 8.30-8.32 (m, 4H), 8.73 (d, J=5.0 Hz,1H), 8.79 (d, J=8.3 Hz, 1H), 8.84 (d, J=8.2 Hz, 1H), 8.90 (s, 1H), 9.14(s, 1H).

Experiment Example 24

In a stream of argon, 8.00 g (17.1 mmol) of2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine, 3.80 g (17.1 mmol) of9-phenanthreneboronic acid and 198 mg (0.171 mmol) oftetrakis(triphenylphosphine)palladium were suspended in a mixed solventcomposed of 600 mL of toluene and 80 mL of ethanol, and the resultantsuspension was heated to 50° C. To the suspension, 51.4 mL (51.4 mmol)of an aqueous 1M K₂CO₃ solution was gradually added dropwise, and themixture was stirred for 15 hours. Then the resultant reaction mixturewas cooled to room temperature, and was then distilled under a reducedpressure to remove all volatile materials. The obtained concentrate waspurified to remove inorganic ingredients by silica gel chromatographyusing a hexane/chloroform (1/1) mixed solvent as an eluent to give 9.59g of a mixture containing4,6-diphenyl-2-[5-(9-phenanthryl)-3-bromophenyl]-1,3,5-triazine.

In a stream of argon, 2.00 g of the obtained mixture containing4,6-diphenyl-2-[5-(9-phenanthryl)-3-bromophenyl]-1,3,5-triazine, 1.35 g(5.31 mmol) of bispinacolatediboron, 1.04 g (10.6 mmol) of potassiumacetate and 128 mg (0.142 mmol) ofdichlorobistriphenylphosphinepalladium were suspended in 70 mL oftetrahydrofuran, and the resultant suspension was stirred at 70° C. for5 hours. Then the resultant reaction mixture was cooled to roomtemperature, and was then distilled under a reduced pressure to removeall volatile materials. The obtained concentrate was purified to removeinorganic ingredients by silica gel chromatography using ahexane/chloroform (1:1) mixed solvent as an eluent to give 1.50 g of amixture containing4,6-diphenyl-2-[5-(9-phenanthryl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-1,3,5-triazine.

In a stream of argon, 0.50 g of the obtained mixture containing4,6-diphenyl-2-[5-(9-phenanthryl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-1,3,5-triazine,288 mg (1.22 mmol) of 6-bromo-2,2′-bipiridine and 47.3 mg (0.0409 mmol)of tetrakis(triphenylphosphine)palladium were suspended in 25 mL oftoluene. To the suspension, 10 mL (20 mmol) of an aqueous 2M Na₂CO₃solution was added, and the obtained mixture was stirred at 90° C. for15 hours. Then the resultant reaction mixture was cooled to roomtemperature, and was then distilled under a reduced pressure to removean organic phase. The obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1/2) mixed solvent as aneluent to give 0.46 g of the target2-[3-(2,2′-bipyridin-6-yl)-5-(9-phenanthryl)phenyl]-4,6-diphenyl-1,3,5-triazine.

¹H-NMR (CDCl₃): δ.7.38 (brs, 1H), 7.59-7.66 (m, 7H), 7.73 (t, J=7.7 Hz,1H), 7.75-7.78 (m, 2H), 7.89 (brs, 1H), 7.96 (s, 1H), 8.02-8.11 (m, 5H),8.55 (brs, 1H), 8.66 (s, 1H), 8.76 (brd, J=7.9 Hz, 2H), 8.84 (d, J=7.7Hz, 2H), 8.85 (d, J=7.8 Hz, 4H), 8.90 (d, J=8.4 Hz, 1H), 9.04 (s, 1H),9.71 (s, 1H).

The obtained triazine derivative exhibited a Tg of 122° C.

Experiment Example 25

In a stream of argon, 143 mg (0.644 mmol) of 9-phenanthreneboronic acid,300 mg (0.644 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazineand 7.44 mg (0.00644 mmol) of tetrakis(triphenylphosphine)palladium weresuspended in a mixed solvent composed of 24 mL of toluene and 3 mL ofethanol, and the resultant suspension was heated to 60° C. To thesuspension, 1.93 mL (1.93 mmol) of an aqueous 1M K₂CO₃ solution wasgradually added dropwise, and the mixture was stirred for 3 hours. Theresultant reaction mixture was cooled to room temperature, and then,0.961 g (4.83 mmol) of2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-pyrimidine and9.66 mL (9.66 mmol) of an aqueous 1M K₂CO₃ solution were added to thereaction mixture. The resultant mixture was heated to 70° C., andmaintained at that temperature for 19 hours while being stirred. Theobtained reaction mixture was cooled to room temperature, and thendistilled under a reduced pressure to remove all volatile materials.Methanol was added to the concentrate, and the thus-deposited solid wascollected by filtration. The obtained crude product was purified bysilica gel chromatography using a hexane/chloroform (1:2) mixed solventas an eluent to give 214 mg of the target4,6-diphenyl-2-[5-(9-phenanthryl)-4′-(2-pyrimidyl)biphenyl-3-yl]-1,3,5-triazineas a white solid (yield: 52%).

¹H-NMR (CDCl₃): δ7.22 (t, J=4.8 Hz, 1H), 7.54-7.63 (m, 7H), 7.67 (t,J=7.4 Hz, 1H), 7.73 (t, J=7.6 Hz, 2H), 7.90 (s, 1H), 7.96-7.99 (m, 3H),8.03 (d, J=8.4 Hz, 1H), 8.10 (s, 1H), 8.62 (d, J=8.7 Hz, 2H), 8.79 (d,J=8.3 Hz, 2H), 8.79 (d, J=8.0 Hz, 2H), 8.79-8.80 (m, 1H), 8.85 (d, J=4.9Hz, 2H), 8.84-8.86 (m, 1H) 8.95 (s, 1H), 9.19 (s, 1H).

Experiment Example 26

In a stream of argon, 77.6 mg (0.167 mmol) of 2-phenanthreneboronicacid, 37 mg (0.167 mmol) of2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine and 5.78 mg (0.0050mmol) of tetrakis(triphenylphosphine)palladium were suspended in a mixedsolvent composed of 7 mL of toluene and 0.8 mL of ethanol, and theresultant suspension was heated to 50° C. To the suspension, 0.50 mL(0.50 mmol) of an aqueous 1M K₂CO₃ solution was gradually addeddropwise, and the mixture was stirred for 2 hours. The resultantreaction mixture was cooled to room temperature, and then, 49.8 mg (0.25mmol) of 4-(2-pyridyl)phenylboronic acid and 0.50 mL (0.50 mmol) of anaqueous 1M K₂CO₃ solution were added to the reaction mixture. Theresultant mixture was heated to 60° C., and maintained at thattemperature for 17 hours while being stirred. The obtained reactionmixture was cooled to room temperature, and then distilled under areduced pressure to remove all volatile materials. Methanol was added tothe concentrate, and the thus-deposited solid was collected byfiltration. The obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:2) mixed solvent as aneluent to give 30 mg of the target4,6-diphenyl-2-[5-(2-phenanthryl)-4′-(2-pyrimidyl)biphenyl-3-yl]-1,3,5-triazineas a white solid (yield: 28%).

¹H-NMR (CDCl₃): δ.7.26-7.30 (m, 1H), 7.52-7.66 (m, 7H), 7.69-7.72 (m,1H), 7.77-7.85 (m, 3H), 7.89 (d, J=8.9 Hz, 1H), 7.95 (t, J=7.1 Hz, 1H),7.96 (d, J=8.5 Hz, 2H), 8.11 (d, J=8.5 Hz, 2H), 8.20 (d, J=8.6 Hz, 2H),8.24 (s, 1H), 8.29 (s, 1H), 8.74-8.76 (m, 2H), 8.81 (d, J=Hz, 2H), 8.82(d, J=Hz, 2H), 8.84 (d, J=8.8 Hz, 1H), 9.06 (s, 1H), 9.12 (s, 1H).

Experiment Example 27

eluent to give 2.50 g of the target4,6-diphenyl-2-[5-(9-phenanthryl)-3′-(2-pyridyl)biphenyl-3-yl]-1,3,5-triazine as a white solid (yield: 37%).

¹H-NMR (CDCl₃): δ.6.7.53-7.62 (m, 8H), 7.67 (t, J=7.7 Hz, 2H), 7.23 (t,J=8.2 Hz, 1H), 7.78 (t, J=7.9 Hz, 1H), 7.84 (d, J=7.9 Hz, 1H), 7.90 (s,1H), 7.90 (d, J=8.4 Hz, 1H), 7.98 (d, J=7.8 Hz, 1H), 8.03 (d, J=8.2 Hz,1H), 8.06 (d, J=7.8 Hz, 1H), 8.11 (s, 1H), 8.42 (s, 1H), 8.72 (d, J=4.9Hz, 1H), 8.79 (d, J=8.3 Hz, 2H), 8.79 (d, J=8.2 Hz, 2H), 8.79 (m, 2H),8.85 (d, J=8.2 Hz, 1H), 8.95 (s, 1H), 9.17 (s, 1H).

The obtained triazine derivative exhibited a Tg of 115° C.

Experiment Example 28

In a stream of argon, 0.95 g (4 mmol) of 9,9-dimethyl-2-fluoreneboronicacid, 1.87 g (4 mmol) of2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine and 46.2 mg (0.04mmol) of tetrakis(triphenylphosphine)palladium were suspended in a mixedsolvent composed of 150 mL of toluene and 20 mL of ethanol, and the

In a stream of argon, 5.00 g (10.7 mmol) of 9-phenanthreneboronic acid,2.38 g (10.7 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazineand 124 mg (0.107 mmol) of tetrakis(triphenylphosphine)palladium weresuspended in a mixed solvent composed of 400 mL of toluene and 50 mL ofethanol, and the resultant suspension was heated to 50° C. To thesuspension, 32.1 mL (32.1 mmol) of an aqueous 1M K₂CO₃ solution wasgradually added dropwise, and the mixture was stirred for 3 hours. Theresultant reaction mixture was cooled to room temperature, and then,3.19 g (10.7 mmol) of 3-(2-pyridyl)phenylboronic acid and 32.1 mL (32.1mmol) of an aqueous 1M K₂CO₃ solution were added to the reactionmixture. The resultant mixture was heated to 60° C., and maintained atthat temperature for 15 hours while being stirred. The obtained reactionmixture was cooled to room temperature, and then distilled under areduced pressure to remove all volatile materials. Methanol was added tothe concentrate, and the thus-deposited solid was collected byfiltration. The obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:2) mixed solvent as anresultant suspension was heated to 50° C. To the suspension, 12 mL (12mmol) of an aqueous 1M K₂CO₃ solution was gradually added dropwise, andthe mixture was stirred for 18 hours. The resultant reaction mixture wascooled to room temperature, and then, 1.19 g (6 mmol) of4-(2-pyridyl)phenylboronic acid and 12 mL (12 mmol) of an aqueous 1MK₂CO₃ solution were added to the reaction mixture. The resultant mixturewas heated to 60° C., and maintained at that temperature for 2 hourswhile being stirred. The obtained reaction mixture was cooled to roomtemperature, and then distilled under a reduced pressure to remove allvolatile materials. Methanol was added to the concentrate, and thethus-deposited solid was collected by filtration. The obtained crudeproduct was purified by silica gel chromatography using ahexane/chloroform (1:2) mixed solvent as an eluent to give 1.61 g of thetarget2-[5-(9,9-dimethylfluoren-2-yl)-4′-(2-pyridyl)biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazineas a white solid (yield: 61.5%).

¹H-NMR (CDCl₃): δ.1.63 (s, 6H), 7.31 (dd, J=7.0, 4.8, 1H), 7.38-7.44 (m,2H), 7.52 (d, J=6.5, H), 7.60-7.68 (m, 6H), 7.81-7.88 (m, 5H), 7.93 (d,J=7.8, 1H), 7.98 (d, J=8.5, 2H), 8.17 (s, H), 8.23 (d, J=8.5, 2H), 8.78(d, J=4.8, 1H), 8.85 (d, J=8.1, 4H), 9.07 (s, 2H).

The obtained triazine derivative exhibited a Tg of 118° C.

Experiment Example 29

In a stream of argon, 0.71 g (3 mmol) of 9,9-dimethyl-2-fluoreneboronicacid, 1.4 g (3 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenylpyrimidine and34.7 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium weresuspended in a mixed solvent composed of 115 mL of toluene and 15 mL ofethanol, and the resultant suspension was heated to 50° C. To thesuspension, 9 mL (9 mmol) of an aqueous 1M K₂CO₃ solution was graduallyadded dropwise, and the mixture was stirred for 18 hours. The resultantreaction mixture was cooled to room temperature, and then, 0.896 g (4.5mmol) of 4-(2-pyridyl)phenylboronic acid and 9 mL (9 mmol) of an aqueous1M K₂CO₃ solution were added to the reaction mixture. The resultantmixture was heated to 60° C., and maintained at that temperature for 3.5hours while being stirred. The obtained reaction mixture was cooled toroom temperature, and then distilled under a reduced pressure to removeall volatile materials. Methanol was added to the concentrate, and thethus-deposited solid was collected by filtration. The obtained crudeproduct was purified by silica gel chromatography using ahexane/chloroform (1:2) mixed solvent as an eluent to give 0.85 g of thetarget2-[5-(9,9-dimethylfluoren-2-yl)-4′-(2-pyridyl)biphenyl-3-yl]-4,6-diphenylpyrimidineas a white solid (yield: 43.3%).

¹H-NMR (CDCl₃): δ.1.63 (s, 6H), 7.30 (d, J=5.7 Hz, 1H), 7.34-7.42 (m,2H), 7.52 (d, J=6.6 Hz, 1H), 7.59-7.64 (m, 6H), 7.82-7.92 (m, 6H), 7.98(d, J=8.4 Hz, 2H), 8.10 (d, J=6.8 Hz, 2H), 8.21 (d, J=8.4 Hz, 2H), 8.37(d, J=6.3 Hz, 4H), 8.78 (d, J=4.8 Hz, 1H), 9.04 (s, 2H).

Experiment Example 30

In a stream of argon, 185 mg (0.644 mmol) of9,9-dimethyl-2-benzo(c)fluoreneboronic acid, 300 mg (0.644 mmol) of2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine and 7.44 mg (0.00644mmol) of tetrakis(triphenylphosphine)palladium were suspended in a mixedsolvent composed of 24 mL of toluene and 3 mL of ethanol, and theresultant suspension was heated to 50° C. To the suspension, 1.93 mL(1.93 mmol) of an aqueous 1M K₂CO₃ solution was gradually addeddropwise, and the mixture was stirred for 3 hours. The resultantreaction mixture was heated to 80° C. and further stirred for 3 hours.The reaction mixture was cooled to room temperature, and then, 256 mg(1.29 mmol) of 4-(2-pyridyl)phenylboronic acid and 2.90 mL (2.90 mmol)of an aqueous 1M K₂CO₃ solution were added to the reaction mixture. Theresultant mixture was heated to 80° C., and maintained at thattemperature for 24 hours while being stirred. The obtained reactionmixture was cooled to room temperature, and then distilled under areduced pressure to remove all volatile materials. Methanol was added tothe concentrate, and the thus-deposited solid was collected byfiltration. The obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:2) mixed solvent as aneluent to give 172 mg of the target2-[5-(9,9-dimethylbenzo(c)fluoren-2-yl)-4′-(2-pyridyl)biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazine as a white solid (yield:38.0%).

¹H-NMR (CDCl₃): δ.1.63 (s, 6H), 7.25-7.29 (m, 1H), 7.42 (t, J=7.4 Hz,1H), 7.49-7.64 (m, 9H), 7.69-7.73 (m, 1H), 7.74 (s, 1H), 7.79 (t, J=8.1Hz, 1H), 7.83 (d, J=7.7 Hz, 1H), 7.97 (d, J=8.7 Hz, 2H), 8.08 (s, 1H),8.11 (d, J=7.8 Hz, 1H), 8.20 (d, J=8.6 Hz, 2H), 8.43 (d, J=7.8 Hz, 1H),8.75 (d, J=4.9 Hz, 1H), 8.79 (d, J=8.3 Hz, 2H), 8.80 (d, J=8.1 Hz, 2H),8.91 (d, J=8.5 Hz, 1H), 8.94 (s, 1H), 9.18 (s, 1H).

Experiment Example 31

In a stream of argon, 0.538 g (2.42 mmol) of 9-phenanthreneboronic acid,1.20 g (2.42 mmol) of2-(3,5-dibromophenyl)-4,6-di-p-tolyl-1,3,5-triazine and 28.0 mg (0.0242mmol) of tetrakis(triphenylphosphine)palladium were suspended in a mixedsolvent composed of 90 mL of toluene and 10 mL of ethanol, and theresultant suspension was heated to 50° C. To the suspension, 7.26 mL(7.26 mmol) of an aqueous 1M K₂CO₃ solution was gradually addeddropwise, and the mixture was stirred for 3 hours. The resultantreaction mixture was cooled to room temperature, and then, 0.722 g (3.63mmol) of 4-(2-pyridyl)phenylboronic acid and 7.26 mL (7.26 mmol) of anaqueous 1M K₂CO₃ solution were added to the reaction mixture. Theresultant mixture was heated to 60° C., and maintained at thattemperature for 15 hours while being stirred. The obtained reactionmixture was cooled to room temperature, and then distilled under areduced pressure to remove all volatile materials. Methanol was added tothe concentrate, and the thus-deposited solid was collected byfiltration. The obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:2) mixed solvent as aneluent to give 0.680 g of the target4,6-di-p-tolyl-2-[5-(9-phenanthryl)-4′-(2-pyridyl)biphenyl-3-yl]-1,3,5-triazine as a white solid (yield: 42%).

¹H-NMR (CDCl₃): δ.2.47 (s, 6H), 7.25-7.28 (m, 1H), 7.35 (d, J=8.0 Hz,4H), 7.60 (t, J=7.7 Hz, 1H), 7.67 (t, J=7.4 Hz, 1H), 7.73 (t, J=7.4 Hz,1H), 7.73 (t, J=7.4 Hz, 1H), 7.79 (t, J=7.8 Hz, 1H), 7.83 (d, J=7.8 Hz,1H), 7.90 (s, 1H), 7.95 (d, J=8.4 Hz, 2H), 7.98 (d, J=8.0 Hz, 1H), 8.04(d, J=7.9 Hz, 1H), 8.07 (s, 1H), 8.18 (d, J=8.5 Hz, 2H), 8.66 (d, J=8.1Hz, 4H), 8.74 (d, J=5.0 Hz, 1H), 8.79 (d, J=8.4 Hz, 1H), 8.85 (d, J=8.0Hz, 1H), 8.92 (s, 1H), 9.16 (s, 1H).

Experiment Example 32

In a stream of argon, 0.71 g (3.21 mmol) of 9-phenanthreneboronic acid,1.50 g (3.21 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazineand 37.0 mg (0.0321 mmol) of tetrakis(triphenylphosphine)palladium weresuspended in a mixed solvent composed of 120 mL of toluene and 15 mL ofethanol, and the resultant suspension was heated to 60° C. andmaintained at that temperature for 12 hours while being stirred. Theobtained reaction mixture was cooled to room temperature, and thendistilled under a reduced pressure to remove all volatile materials.Methanol was added to the concentrate, and the thus-deposited solid wascollected by filtration. The obtained crude product was purified bysilica gel chromatography using a hexane/chloroform (2:1) mixed solventas an eluent to give 0.54 g of the target4,6-diphenyl-2-[5-(9-phenanthryl)-3-bromophenyl]-1,3,5-triazine as awhite solid (yield: 30%).

¹H-NMR (CDCl₃): δ. 7.57-7.76 (m, 10H), 7.82 (s, 1H), 7.93-7.89 (m, 3H),8.78 (d, J=8.0 Hz, 4H), 8.80 (d, J=8.2 Hz, 1H), 8.85 (d, J=8.2 Hz, 1H),8.90 (s, 1H), 9.02 (s, 1H).

Experiment Example 33 Measurement of Tg of2-{4,4″-di(2-pyridyl)-[1,1′:3′,1″]-terphenyl-5′-yl}-4,6-di-p-tolyl-1,3,5-triazine

Thermal analysis of 2-{4,4″-di(2-pyridyl)-[l,1′:3′,1″]-terphenyl-5′-yl}-4,6-di-p-tolyl-1,3,5-triazine, which isdescribed in patent document 1, revealed that its Tg was 108° C.

Experiment Example 34

In a stream of argon, 195 mg of4,6-bis(4-tert-butylphenyl)-2-(3,5-dibromophenyl)-1,3,5-triazine, 188 mgof bispinacolatediboron, 159 mg of potassium acetate and 9.48 mg ofdichlorobistriphenylphosphinepalladium were suspended in 10 mL oftetrahydrofuran, and the obtained suspension was heated under reflux for38 hours. The obtained reaction mixture was cooled to room temperature,and then distilled under a reduced pressure to remove all volatilematerials. The obtained crude product was purified by silica gelchromatography using chloroform as an eluent and washed with hexane togive 170 mg of4,6-bis(4-tert-butylphenyl)-2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-1,3,5-triazineas a yellow solid (yield: 75%).

¹H-NMR (CDCl₃): δ1.43 (s, 18H), 1.44 (s, 24H), 7.64 (d, J=8.6 Hz, 4H),8.52 (t, J=1.2 Hz, 1H), 8.74 (d, J=8.6 Hz, 4H), 9.23 (d, J=1.2 Hz, 2H).

Experiment Example 35

In a stream of argon, 1.00 g of2-(3,5-dibromophenyl)-4,6-di(2-naphthyl)-1,3,5-triazine, 996 mg ofbispinacolatediboron, 830 mg of potassium acetate and 61.8 mg ofdichlorobistriphenylphosphinepalladium were suspended in 50 mL oftetrahydrofuran, and the obtained suspension was heated under reflux for41 hours. The obtained reaction mixture was cooled to room temperature,and then distilled under a reduced pressure to remove all volatilematerials. The thus-obtained crude product was purified by silica gelchromatography using chloroform as an eluent to give 1.01 mg of2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-4,6-di(2-dinaphthyl)-1,3,5-triazineas a yellow solid (yield: 87%).

¹H-NMR (CDCl₃): δ1.37 (s, 24H), 7.51-7.57 (m, 4H), 7.89 (brd, J=7.7 Hz,2H), 8.01 (d, J=8.7 Hz, 2H), 8.09 (brd, J=7.7 Hz, 2H), 8.48 (t, J=1.2Hz, 1H), 8.85 (dd, J=8.7, 1.7 Hz, 2H), 9.24 (d, J=1.2 Hz, 2H), 9.36(brs, 2H).

Experiment Example 36

In a stream of argon, 300 mg of2,4-bis(4-biphenylyl)-6-(3,5-dibromophenyl)-1,3,5-triazine, 270 mg ofbispinacolatediboron, 228 mg of potassium acetate and 17.0 mg ofdichlorobistriphenylphosphinepalladium were suspended in 20 mL ofdioxane, and the obtained suspension was heated under reflux for 24hours. The obtained reaction mixture was cooled to room temperature, andthen distilled under a reduced pressure to remove all volatilematerials. The thus-obtained crude product was purified by silica gelchromatography using chloroform as an eluent and then washed with hexaneto give 250 mg of4,6-bis(4-biphenylyl)-2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-1,3,5-triazineas a yellow solid (yield: 72%).

¹H-NMR (CDCl₃): δ1.45 (s, 24H), 7.44 (brt, J=7.4 Hz, 2H), 7.54 (t, J=7.4Hz, 4H), 7.76 (d, J=7.4 Hz, 4H), 7.87 (d, J=8.5 Hz, 4H), 8.56 (t, J=1.2Hz, 1H), 8.93 (d, J=8.5 Hz, 4H), 9.28 (d, J=1.2 Hz, 2H).

Experiment Example 37

5.97 g of 3,5-dibromobenzoyl chloride and 4.12 g of benzonitrile weredissolved in 50 mL of chloroform, and the obtained solution was cooledto 0° C. 5.98 g of antimony pentachloride was added dropwise to thecooled solution. The obtained mixed liquid was stirred at roomtemperature for 10 minutes, and then, heated under reflux for 22 hours.The obtained reaction mixture was cooled to room temperature, and thendistilled under a reduced pressure to remove chloroform to give a yellowsolid.

The yellow solid was added to 300 mL of aqueous 28% ammonia maintainedat 0° C. to give a white solid. The aqueous liquid was stirred at roomtemperature for 1 hour and then filtered. The obtained white solidproduct was washed with water and then with methanol. The thus-obtainedwhite solid was purified by silica gel chromatography to give 6.32 g of2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine as a white solid(yield: 68%).

¹H-NMR (CDCl₃): δ7.56-7.61 (m, 4H), 7.61-7.67 (m, 2H), 7.90 (t, J=1.8Hz, 1H), 8.72-8.78 (m, 4H), 8.82 (d, J=1.8 Hz, 2H).

¹³C-NMR (CDCl₃): δ123.4, 128.8, 129.1, 130.6, 133.0, 135.7, 137.6,139.8, 169.3, 172.0.

Experiment Example 38

2.98 g of 3,5-dibromobenzoyl chloride and 3.18 g of4-tert-butylbenzonitrile were dissolved in 30 mL of chloroform. Theobtained solution was cooled to 0° C., and 2.99 g of antimonypentachloride was added dropwise to the cooled solution. The obtainedmixed liquid was stirred at room temperature for 10 minutes, and then,heated under reflux for 17 hours. The obtained reaction mixture wascooled to room temperature, and then distilled under a reduced pressureto remove chloroform to give a solid product.

The solid product was added to 200 mL of aqueous 28% ammonia maintainedat 0° C. to give a white precipitate. The aqueous liquid was stirred atroom temperature for 1 hour and then filtered. The obtained whiteprecipitate was washed with water and then with methanol. Thethus-obtained white precipitate was purified by silica gelchromatography to give 4.46 g of4,6-bis(4-tert-butylphenyl)-2-(3,5-dibromophenyl)-1,3,5-triazine as awhite solid (yield: 77%).

¹H-NMR (CDCl₃): δ1.41 (s, 18H), 7.61 (d, J=8.5 Hz, 4H), 7.88 (t, J=1.8Hz, 1H), 8.65 (d, J=8.5 Hz, 4H), 8.80 (d, J=1.8 Hz, 2H).

¹³C-NMR (CDCl₃): δ31.2, 35.1, 123.3, 125.7, 128.9, 130.5, 133.1, 137.4,140.0, 156.5, 169.0, 171.8.

Experiment Example 39

In a stream of argon, a three-necked reaction flask equipped with areflux condenser and a mechanical stirrer was charged with 19.9 g of3,5-dibromobenzoyl chloride and 20.4 g of 2-cyanonaphthalene, and then,180 mL of chlorobenzene was added to the content. The obtained solutionwas cooled to 0° C., and 19.9 g of antimony pentachloride was addeddropwise to the solution. The obtained mixture was stirred at roomtemperature for 30 minutes, and further stirred at 100° C. for 2 hours.The thus-obtained dark red suspension was cooled to −20° C., and 100 mLof 28% aqueous ammonia was added to the cooled suspension. The obtainedmilky white suspension was stirred at room temperature for 1 hour, andthen heated to 140° C. to remove 70 mL of the organic solvent and 30 mLof water. The reaction mixture was left to stand and filtered.

The obtained solid was suspended in 100 mL of chlorobenzene. Thesuspension was heated to 130° C. and filtered to remove insolubles. Thisprocedure of suspending in 100 mL of chlorobenzene, followed by heatingand filtration to remove insolubles was repeated further 3 times. Thefiltrates were left to stand, and joined together. 400 mL of methanolwas added to the joined filtrate to precipitate. The precipitate wascollected by filtration, and washed with 300 mL of methanol two times.The precipitate was dried to give 7.90 g of4,6-di(2-dinaphthyl)-2-(3,5-dibromophenyl)-1,3,5-triazine as a whitepowder (yield: 14%).

The insolubles obtained by heating and filtration of the suspension inchloroform were subjected to extraction using a soxhlet extractor andchloroform as extracting solvent to give 5.40 g of2-(3,5-dibromophenyl)-4,6-di(2-dinaphthyl)-1,3,5-triazine as a whitepowder (yield: 9.5%).

¹H-NMR (CDCl₃): δ7.60-7.69 (m, 4H), 7.94 (s, 1H), 7.98 (d, J=7.8 Hz,2H), 8.06 (d, J=8.6 Hz, 2H), 8.17 (d, J=7.8 Hz, 2H), 8.83 (d, J=8.6 Hz,2H), 8.90 (s, 2H), 9.34 (s, 2H).

Experiment Example 40

2.98 g of 3,5-dibromobenzoyl chloride and 3.58 g of4-biphenylcarbonitrile were dissolved in 40 mL of chloroform. Theobtained solution was cooled to 0° C., and 2.99 g of antimonypentachloride was added dropwise to the cooled solution. The obtainedmixed liquid was stirred at room temperature for 10 minutes, and then,heated under reflux for 14 hours. The obtained reaction mixture wascooled to room temperature, and then distilled under a reduced pressureto remove chloroform to give4,6-bis(4-biphenylyl)-2-(3,5-dibromophenyl)-1,3,5-oxadiazin-1-ium=hexachloroantimonateas a red solid.

The obtained red solid was added to 150 mL of aqueous 28% ammoniamaintained at 0° C. to give a white precipitate. The aqueous liquid wasstirred at room temperature for 1 hour and then filtered. The obtainedwhite precipitate was washed with water and then with methanol. Thethus-obtained white precipitate was dried, and then suspended in 200 mLof chloroform. The suspension was heated and then filtered. Theinsolubles collected by filtration were suspended in 150 mL ofchloroform and the obtained suspension was filtered. This procedure ofsuspending in 150 mL of chloroform, followed by heating and filtrationwas repeated 3 times. All of the filtrates were joined together, andthen distilled under reduced pressure to remove chloroform. Thethus-obtained solid product was recrystallized fromdichloromethane-methanol to give 5.14 g of4,6-bis(4-biphenylyl)-2-(3,5-dibromophenyl)-1,3,5-triazine as a whitesolid (yield: 83%).

¹H-NMR (CDCl₃): δ7.40-7.45 (m, 2H), 7.49-7.54 (m, 4H), 7.70-7.75 (m,4H), 7.83 (d, J=8.5 Hz, 4H), 7.91 (t, J=1.8 Hz, 1H), 8.83 (d, J=8.5 Hz,4H), 8.85 (d, J=1.8 Hz, 2H).

¹³C-NMR (CDCl₃): δ123.4, 127.3, 127.5, 128.2, 129.0, 129.7, 130.7,134.7, 137.6, 139.9, 140.3, 145.7, 169.3, 171.8.

Experiment Example 41

4.10 g of 3,5-dibromobenzoyl chloride and 5.00 g of3-biphenylcarbonitrile were dissolved in 100 mL of chloroform in astream of argon. The obtained solution was cooled to 0° C., and 4.20 gof antimony pentachloride was added dropwise to the cooled solution. Theobtained mixed liquid was stirred at room temperature for 1 hour, andthen, heated under reflux for 12 hours. The obtained reaction mixturewas cooled to room temperature, and then distilled under a reducedpressure to remove all volatile materials to give a red solid.

The obtained red solid was pulverized in a stream of argon and added toaqueous 28% ammonia maintained at 0° C. The thus-obtained suspension wasfurther stirred at room temperature for 1 hour and then filtered. Theobtained precipitate was washed with water and then with methanol. Thethus-obtained precipitate was dried, and then subjected to extractionusing a soxhlet extractor and chloroform as extracting solvent. Theextracted liquid was left to stand to be thereby cooled, and thedeposited solid was collected by filtration. The obtained solid wasdried to give 2.80 g of4,6-bis(3-biphenylyl)-2-(3,5-dibromophenyl)-1,3,5-triazine as a whitepowder (yield: 32%).

¹H-NMR (CDCl₃): δ7.46 (brt, J=7.4 Hz, 2H), 7.52-7.58 (m, 4H), 7.67 (dd,J=7.8 Hz, 7.7 Hz, 2H), 7.76 (brd, J=7.7 Hz, 4H), 7.86 (d, J=7.7 Hz, 2H),7.90 (brd, 1H), 8.72 (d, J=7.8 Hz, 2H), 8.81 (d, J=1.8 Hz, 2H), 8.95 (s,2H).

¹³C-NMR (CDCl₃): δ123.4, 127.4, 127.7, 127.8, 128.1, 130.7, 131.7,136.2, 137.7, 139.7, 140.7, 141.9, 169.4, 172.0.

Experiment Example 42

In a stream of argon, 89 mL of a 1.57M tert-butyllithium pentanesolution was dissolved in 32 mL of tetrahydrofuran, and the solution wascooled to −78° C. 10.0 g of 2-bromopyridine was added dropwise to thesolution, and the mixture was stirred for 1.5 hours. 42.5 g ofdichloro(tetramethylethylenediamine) zinc was added to the mixture, andthe temperature of the resultant mixture was elevated to roomtemperature, and the mixture was further stirred for 1 hour. To theresultant mixture, a suspension of 10.0 g of 1,3,5-tribromobezene and734 mg of tetrakis(triphenylphosphine)palladium in 64 mL oftetrahydrofuran was added. The obtained mixture was heated under refluxfor 17 hours while being stirred. Then the obtained reaction mixture wascooled to room temperature, and was then distilled under a reducedpressure to remove all volatile materials. Water and chloroform wereadded to the concentrate, and the organic phase was separated anddistilled to remove the solvent. The thus-obtained crude product waspurified by silica gel chromatography using an ethyl acetate/hexane(2:8-1:1) mixed solvent to give 6.5 g of the target3,5-di(2-pyridyl)bromobenzene as a yellow solid (yield: 66%).

¹H-NMR (CDCl₃): δ7.22 (dd, J=8.6, 5.8, 2H), 7.77-7.80 (m, 4H), 8.16 (s,2H), 8.50 (t, J=1.6 Hz, 1H), 8.66 (d, J=4.8 Hz, 2H).

Experiment Example 43

In a stream of argon, 3.80 g of phenylboronic acid, 8.15 g of2-(3,5-dibromophenyl)pyridine and 1.20 g oftetrakis(triphenylphosphine)palladium were suspended in a mixed solventcomprised of 26 mL of an aqueous 2M sodium carbonate solution, 26 mL ofethanol and 52 mL of toluene, and the obtained mixture was distilledunder reflux for 22 hours. The resultant reaction mixture was cooled toroom temperature, and then distilled under a reduced pressure to removeall volatile materials. Water and chloroform were added to theconcentrate, and the organic phase was separated and distilled to removethe solvent. The thus-obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:1) mixed solvent as aneluent to give 3.95 g of 2-(3-bromophenyl-5-yl)pyridine as a yellowliquid (yield: 43%).

In a stream of argon, 3.95 g of 2-(3-bromophenyl-5-yl)pyridine, 3.37 gof bispinacolatediboron, 3.26 g of potassium acetate and 0.31 g ofdichlorobistriphenylphosphinepalladium were suspended in 60 mL oftetrahydrofuran, and the suspension was heated under reflux for 43hours. The obtained reaction mixture was cooled to room temperature, andwas then distilled under a reduced pressure to remove all volatilematerials. The thus-obtained crude product was purified by silica gelchromatography using chloroform as an eluent to give 1.55 g of thetarget2-[3-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)-biphenyl-5-yl]pyridineas a yellow solid (yield: 99%).

¹H-NMR (CDCl₃): δ1.31 (s, 12H), 7.16-7.20 (m, 1H), 7.28 (tt, J=7.4, 1.2Hz, 1H), 7.36-7.39 (m, 1H), 7.65 (dd, J=8.3, 1.2 Hz, 1H), 7.70 (dd,J=7.5, 1.8 Hz, 1H), 7.78 (dt, J=8.0, 1.0 Hz, 1H), 8.03 (dd, J=1.9, 1.0Hz, 1H), 8.29-8.30 (m, 1H), 8.31 (t, J=1.9 Hz, 1H), 8.65 (ddd, J=4.8,1.8, 0.9 Hz, 1H).

Experiment Example 44

In a stream of argon, 1.00 g of2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-4,6-diphenyl-1,3,5-trizine,1.33 g of 4′-bromo-2,2′:6′,2″-terpyridine and 165 mg oftetrakis(triphenylphosphine)palladium were suspended in a mixed solventcomprised of 20 mL of an aqueous 2M sodium carbonate solution and 50 mLof toluene, and the obtained mixture was distilled under reflux for 45hours. The resultant reaction mixture was cooled to room temperature,and then distilled under a reduced pressure to remove all volatilematerials. Water was added to the concentrate, and the thus-depositedsolid was collected by filtration and washed with methanol. Thethus-obtained crude product was purified by alumina chromatography usinga hexane/chloroform (1:1-0:1) mixed solvent as an eluent to give 1.20 gof the target2-[3,5-bis(2,2′:6′,2″-terpyridin-4′-yl)phenyl]-4,6-diphenyl-1,3,5-triazineas a white solid (yield: 88%).

¹H-NMR (CDCl₃): δ7.29-7.34 (m, 4H), 7.52-7.55 (m, 6H), 7.85 (ddd, J=7.8,7.8, 1.8 Hz, 4H), 8.46 (t, J=1.6 Hz, 1H), 8.66-8.69 (m, 8H), 8.77-8.80(m, 4H), 8.87 (s, 4H), 9.21 (d, J=1.6 Hz, 2H).

Experiment Example 45

In a stream of argon, 70.0 mg of4,6-bis(4-tert-butylphenyl)-2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-1,3,5-triazine,78.0 mg of 4′-bromo-2,2′:6′,2″-terpyridine and 9.6 mg oftetrakis(triphenylphosphine) palladium were suspended in a mixed solventcomprised of 1 mL of an aqueous 2M sodium carbonate solution and 2 mL oftoluene, and the obtained mixture was distilled under reflux for 66hours. The resultant reaction mixture was cooled to room temperature,and then methanol was added to the reaction mixture. The thus-depositedsolid was collected by filtration, and the obtained crude product waspurified by alumina chromatography using chloroform as an eluent to give49.0 mg of the target4,6-bis(4-tert-butylphenyl)-2-[3,5-bis(2,2′:6′,2″-terpyridin-4′-yl)phenyl]-1,3,5-triazineas a white solid (yield: 53%).

¹H-NMR (CDCl₃): δ1.30 (s, 18H), 7.26 (ddd, J=7.7, 4.2, 1.1 Hz, 4H), 7.49(d, J=8.5 Hz, 4H), 7.80 (ddd, J=7.7, 7.7, 1.7 Hz, 4H), 8.37 (t, J=1.7Hz, 1H), 8.62-8.66 (m, 12H), 8.83 (s, 4H), 9.15 (d, J=1.7 Hz, 2H).

¹³C-NMR (CDCl₃): δ31.3 (CH₃×6), 35.2 (quart.×2), 119.6 (CH×4), 121.5(CH×4), 123.9 (CH×4), 125.7 (CH×4), 128.4 (CH×2), 129.1 (CH×4), 130.3(CH), 133.5 (quart.×2), 136.9 (CH×4), 138.3 (quart.), 140.4 (quart.×2),149.2 (CH×4), 150.1 (quart.×2), 156.1 (quart.×6), 156.2 (quart.×4),171.2 (quart.), 171.8 (quart.×2).

Experiment Example 46

In a stream of argon, 100.0 mg of2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-4,6-di(2-naphthyl)-1,3,5-triazine,133 mg of 4′-bromo-2,2′:6′,2″-terpyridine and 14.0 mg oftetrakis(triphenylphosphine) palladium were suspended in suspended in amixed solvent comprised of 1 mL of an aqueous 2M sodium carbonatesolution and 4 mL of toluene, and the obtained mixture was distilledunder reflux for 59 hours. The resultant reaction mixture was cooled toroom temperature, and then distilled under a reduced pressure to removeall volatile materials. Water was added to the concentrate, and thethus-deposited solid was collected by filtration and washed withmethanol. The thus-obtained crude product was purified by aluminachromatography using a hexane/chloroform (1:2-0:1) mixed solvent as aneluent to give 91.0 mg of the target2-[3,5-bis(2,2′:6′,2″-terpyridin-4′-yl)phenyl]-4,6-di(2-naphthyl)-1,3,5-triazineas a white solid (yield: 69%).

¹H-NMR (CDCl₃): δ7.31 (ddd, J=7.6, 4.8, 1.2 Hz, 4H), 7.47-7.55 (m, 4H),7.85 (ddd, J=7.6, 7.6, 1.8 Hz, 4H), 7.85-7.87 (m, 2H), 7.97 (d, J=8.5Hz, 2H), 8.07 (d, J=7.7 Hz, 2H), 8.48 (t, J=1.7 Hz, 1H), 8.66-8.71 (m,8H), 8.85 (dd, J=8.5, 1.7 Hz, 2H), 8.92 (s, 4H), 9.30 (d, J=1.7 Hz, 2H),9.39 (brs, 2H).

Experiment Example 47

In a stream of argon, 100.0 mg of4,6-bis(3-biphenylyl)-2-[3,5-bis(4,4,5,5-tetramethyl-,3,2-dioxabororan-2-yl)phenyl]-1,3,5-triazine, 105 mg of4′-bromo-2,2′:6′,2″-terpyridine and 12.9 mg oftetrakis(triphenylphosphine)palladium were suspended in a mixed solventcomprised of 1 mL of an aqueous 2M sodium carbonate solution and 3 mL oftoluene, and the obtained mixture was distilled under reflux for 69hours. The resultant reaction mixture was cooled to room temperature,and then distilled under a reduced pressure to remove all volatilematerials. Water was added to the concentrate, and the thus-depositedsolid was collected by filtration and washed with methanol. Thethus-obtained crude product was purified by alumina chromatography usingchloroform as an eluent to give 110 mg of the target4,6-bis(3-biphenylyl)-2-[3,5-bis(2,2′:6′,2″-terpyridin-4′-yl)phenyl]-1,3,5-triazineas a white solid (yield: 85%).

¹H-NMR (CDCl₃): δ7.26-7.32 (m, 10H), 7.61 (t, J=7.7 Hz, 2H), 7.69 (brdd,J=7.9, 1.5 Hz, 4H), 7.79 (brd, J=7.4 Hz, 2H), 7.85 (ddd, J=7.6, 7.6, 1.8Hz, 4H), 8.48 (t, J=1.7 Hz, 1H), 8.64 (ddd, J=4.7, 1.8, 0.8 Hz, 4H),8.68 (brdt, J=7.9, 1.0 Hz, 4H), 8.77 (brdt, J=6.5, 1.6 Hz, 2H), 8.90 (s,4H), 9.03 (t, J=1.6 Hz, 2H), 9.26 (d, J=1.7 Hz, 2H)

¹³C-NMR (CDCl₃): δ119.5 (CH×4), 121.4 (CH×4), 123.9 (CH×4), 127.3(CH×4), 127.5 (CH×2), 127.9 (CH×2), 128.2 (CH×2), 128.6 (CH×2), 128.9(CH×4), 129.2 (CH×2), 130.3 (CH), 131.4 (CH×2), 136.6 (quart.×2), 136.9(CH×4), 137.8 (quart.), 140.3 (quart.×2), 140.7 (quart.×2), 141.6(quart.×2), 149.3 (CH×4), 149.9 (quart.×2), 156.2 (quart.×4), 156.2(quart.×4), 171.3 (quart.), 171.9 (quart.×2).

Experiment Example 48

In a stream of argon, 100.0 mg of4,6-bis(4-biphenylyl)-2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-1,3,5-triazine,105 mg of 4′-bromo-2,2′:6′,2″-terpyridine and 12.9 mg oftetrakis(triphenylphosphine)palladium were suspended in a mixed solventcomprised of 1 mL of an aqueous 2M sodium carbonate solution and 3 mL oftoluene, and the obtained mixture was distilled under reflux for 69hours. The resultant reaction mixture was cooled to room temperature,and then distilled under a reduced pressure to remove all volatilematerials. Water was added to the concentrate, and the thus-depositedsolid was collected by filtration and washed with methanol. Thethus-obtained crude product was purified by alumina chromatography usingchloroform as an eluent to give 110 mg of the target4,6-bis(4-biphenylyl)-2-[3,5-bis(2,2′:6′,2″-terpyridin-4′-yl)phenyl]-1,3,5-triazineas a white solid (yield: 62%).

¹H-NMR (CDCl₃): δ7.29-7.36 (m, 6H), 7.43 (t, J=7.7 Hz, 4H), 7.65 (brd,J=7.7 Hz, 4H), 7.76 (d, J=8.5 Hz, 4H), 7.85 (ddd, J=7.6, 7.6, 1.8 Hz,4H), 8.44 (t, J=1.7 Hz, 1H), 8.67-8.71 (m, 8H), 8.85-8.88 (m, 4H), 8.88(s, 4H), 9.24 (d, J=1.7 Hz, 2H).

Experiment Example 49

In a stream of argon, 3.34 g of 3,5-di(2-pyridyl)bromobenzene wasdissolved in 43 mL of tetrahydrofuran, and then, 7.6 mL of a 1.58Mbuthyllithium hexane solution was added dropwise at −78° C. to theobtained solution. The obtained mixture was stirred at −78° C. for 15minutes, and 3.24 g of dichloro(tetramethylethylenediamine) zinc wasadded to the mixture. The temperature of the obtained mixture waselevated to room temperature, and stirred for 30 minutes. To theobtained mixture, 2.00 g of2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-trizine and 98.9 mg oftetrakis(triphenylphosphine)palladium were added, and the obtainedmixture was distilled under reflux for 19 hours. The resultant reactionmixture was cooled to room temperature, and then distilled under areduced pressure to remove all volatile materials. Methanol was added tothe concentrate, and the thus-deposited solid was collected byfiltration. The thus-obtained crude product was purified by silica gelchromatography using chloroform as an eluent to give 2.10 g of thetarget4,6-diphenyl-2-[3,5,3″,5″-tetra(2-pyridyl)-(1,1′:3′,1″-terphenyl-5′-yl)-1,3,5-triazineas a white solid (yield: 64%).

¹H-NMR (CDCl₃): δ7.32 (dd, J=6.2, 6.1, 4H), 7.55-7.68 (m, 6H), 7.85 (t,J=7.7 Hz, 4H), 8.01 (5, J=8.0 Hz, 4H), 8.33 (s, 1H), 8.51 (s, 4H), 8.76(s, 2H), 8.80 (d, J=4.8, 4H), 8.85 (d, J=8.0 Hz, 4H), 9.14 (s, 2H).

Experiment Example 50

In a stream of argon, 3.34 g of 3,5-di(2-pyridyl)bromobenzene wasdissolved in 43 mL of tetrahydrofuran, and then, 7.6 mL of a 1.58Mbuthyllithium hexane solution was added dropwise at −78° C. to theobtained solution. The obtained mixture was stirred at −78° C. for 15minutes, and 3.25 g of dichloro(tetramethylethylenediamine) zinc wasadded to the mixture. The temperature of the obtained mixture waselevated to room temperature, and stirred for 30 minutes. To theobtained mixture, 2.00 g of 2-(3,5-dibromophenyl)-4,6-diphenylpyrimidineand 98.9 mg of tetrakis(triphenylphosphine)palladium were added, and theobtained mixture was distilled under reflux for 17 hours. The resultantreaction mixture was cooled to room temperature, and then distilledunder a reduced pressure to remove all volatile materials. Methanol wasadded to the concentrate, and the thus-deposited solid was collected byfiltration. The thus-obtained crude product was purified by silica gelchromatography using chloroform as an eluent to give 2.60 g of thetarget4,6-diphenyl-2-(3,5,3″,5″-tetra(2-pyridyl)-(1,1′:3′,1″-terphenyl-5′-yl)-pyrimidineas a white solid (yield: 79%).

¹H-NMR (CDCl₃): δ7.31 (dd, J=6.12, 6.14 Hz, 4H), 7.73-7.64 (m, 6H), 7.84(t, J=7.7 Hz, 4H), 8.00 (d, J=8.0 Hz, 4H), 8.11 (s, 1H), 8.26 (s, 1H),8.36 (d, J=9.6 Hz, 4H), 8.50 (s, 4H), 8.75 (s, 2H), 8.79 (d, J=4.0 Hz,4H), 9.10 (s, 2H).

Experiment Example 51

In a stream of argon, 100.0 mg of2-[3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl]-4,6-diphenylpyrimidine,167 mg of 4′-bromo-2,2′: 6′,2″-terpyridine and 20.6 mg oftetrakis(triphenylphosphine)palladium were suspended in a mixed solventcomprised of 0.8 mL of an aqueous 2M sodium carbonate solution and 5 mLof toluene, and the obtained mixture was distilled under reflux for 86hours. The resultant reaction mixture was left to stand to roomtemperature, and then distilled under a reduced pressure to remove allvolatile materials. Methanol was added to the concentrate, and thethus-deposited solid was collected by filtration and washed with waterand methanol. The thus-obtained crude product was purified by silica gelchromatography using a hexane/chloroform (1:4) mixed solvent as aneluent to give 129 mg of the target2-[3,5-bis(2,2′:6′,2″-terpyridin-4′-yl)phenyl]-4,6-diphenylpyrimidine asa white solid (yield: 94%).

¹H-NMR (CDCl₃): δ7.30 (dd, J=7.5, 2.4, 1.2 Hz, 4H), 7.48-7.54 (m, 6H),7.84 (dd, J=8.0, 7.9, 1.9 Hz, 4H), 8.05 (s, 1H), 8.30 (dd, J=7.9, 1.6Hz, 4H), 8.35 (t, J=1.7 Hz, 1H), 8.65-8.69 (m, 8H), 8.86 (s, 4H), 9.16(d, J=1.7 Hz, 2H).

Experiment Example 52

In a stream of argon, 542 mg of2-[5-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)biphenyl-3-yl]pyridine,329 mg of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine, 494 mg ofcesium carbonate, 6.20 mg of palladium acetate and 26.3 mg of2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were suspended in20 mL of tetrahydrofuran, and the obtained mixture was distilled underreflux for 48 hours. The resultant reaction mixture was left to stand toroan temperature, and then distilled under a reduced pressure to removeall volatile materials. Methanol was added to the concentrate, and thethus-deposited solid was collected by filtration. The thus-obtainedcrude product was purified by silica gel chromatography using ahexane/chloroform (1:1) mixed solvent as an eluent to give 200 mg of thetarget2,4-diphenyl-6-[5′,5″-di(2-pyridyl)-1,1′:3′,1″:3″,1″′:3″′,1″′-quinquephenyl-5″-yl]-1,3,5-triazineas a white powder (yield: 38%).

¹H-NMR (CDCl₃): δ7.22 (ddd, J=7.4, 2.4, 1.1 Hz, 2H), 7.34 (tt, J=7.4,1.2 Hz, 2H), 7.42-7.54 (m, 10H), 7.72-7.76 (m, 6H), 7.84 (dt, J=8.0, 1.0Hz, 2H), 7.98 (dt, J=1.7 Hz, 2H), 8.17 (t, J=1.8 Hz, 1H), 8.25 (t, J=1.6Hz, 2H), 8.30 (t, J=1.6 Hz, 2H), 8.69 (ddd, J=4.8, 0.90, 0.88 Hz, 2H),8.74 (dd, J=8.1, 1.6 Hz, 4H), 9.02 (d, J=1.7 Hz, 2H).

¹³C-NMR (CDCl₃): δ121.0 (CH×2), 122.5 (CH×2), 125.3 (CH×2), 125.4(CH×2), 127.15 (CH×2), 127.23 (CH×2), 127.6 (CH×4), 127.7 (CH×2), 128.7(CH×4), 128.9 (CH×4), 129.2 (CH×4), 130.9 (CH×4), 132.6 (CH), 136.2(quart.×2), 136.9 (CH), 137.7 (quart.), 140.8 (quart.×2), 141.0(quart.×2), 142.2 (quart.×2), 142.60 (quart.×2), 142.62 (quart.×2),149.9 (CH), 157.3 (quart.×2), 171.8 (quart.), 171.9 (quart.×2).

Experiment Example 53

In a stream of argon, 163 g of2-[5-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)biphenyl-3-yl]pyridine,710 mg of 2-(3,5-dibromophenyl)-4,6-diphenylpyrimidine, 1.49 g of cesiumcarbonate, 137 mg of palladium acetate and 58.1 mg of2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were suspended in30 mL of dioxane, and the obtained mixture was distilled under refluxfor 67 hours. The resultant reaction mixture was left to stand to roomtemperature, and then distilled under a reduced pressure to remove allvolatile materials. Methanol was added to the concentrate, and thethus-deposited solid was collected by filtration. The thus-obtainedcrude product was purified by silica gel chromatography using amethanol/chloroform (1:100-1:50) mixed solvent as an eluent to give 975mg of the target4,6-diphenyl-2-[5′,5″′-di(2-pyridyl)-1,1′:3′,1″:3″,1″′:3″′,1″′-quinquephenyl-5″-yl]pyrimidineas a white powder (yield: 83%).

¹H-NMR (CDCl₃): δ7.30-7.33 (m, 2H), 7.43 (t, J=7.3 Hz, 2H), 7.51-7.59(m, 10H), 7.83-7.84 (m, 6H), 7.94 (d, J=7.9 Hz, 2H), 8.09-8.12 (m, 3H),8.19 (bs, 1H), 8.35-8.39 (m, 8H), 8.79 (d, J=4.2 Hz, 2H), 9.09 (bs, 2H).

Experiment Example 54

In a stream of argon, 1.37 g (6.16 mmol) of 9-phenanthreneboronic acid,1.20 g (2.57 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazineand 72.1 mg (0.103 mmol) of dichlorobis(triphenylphosphine)palladiumwere suspended in 75 mL of tetrahydrofuran, and the temperature of theobtained suspension was elevated to 70° C. 4.81 mL (19.3 mmol) of anaqueous 4N NaOH solution was gradually added dropwise to the suspension,and the obtained mixture was distilled under reflux for 5 hours. Theresultant reaction mixture was left to stand to room temperature, andthen distilled under a reduced pressure to remove all volatilematerials. Methanol was added to the concentrate, and the thus-depositedsolid was collected by filtration. The thus-obtained crude product wasrecrystallized from o-xylene to give 1.13 g of the target2-[3,5-di(9-phenanthryl)phenyl]-4,6-diphenyl-1,3,5triazine as grayishwhite solid (yield: 66%).

¹H-NMR (CDCl₃): δ. 7.56 (t, J=7.1 Hz, 4H), 7.61 (t, J=7.3 Hz, 2H), 7.66(t, J=8.2 Hz, 2H), 7.70 (t, J=8.0 Hz, 2H), 7.75 (t, J=8.4 Hz, 2H), 7.76(t, J=8.3 Hz, 2H), 7.97 (s, 2H), 8.02 (d, J=8.0 Hz, 2H), 8.03 (s, 1H),8.18 (d, J=8.1 Hz, 2H), 8.79 (d, J=8.3 Hz, 4H), 8.81 (d, J=8.4 Hz, 2H),8.87 (d, J=8.4 Hz, 2H), 9.09 (s, 2H).

The melting point and Tg of the obtained compound are shown in Table 1,below.

Experiment Example 55

In a stream of argon, 1.00 g (3.28 mmol) of9-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)anthracene, 0.64 g (1.37mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine, 15.38 mg(0.069 mmol) of palladium acetate, and 0.21 mL of a toluene solutioncontaining 0.21 mmol of tri-tert-butylphosphine were suspended in 65 mLof tetrahydrofuran, and the temperature of the obtained suspension waselevated to 70° C. 2.57 mL (10.3 mmol) of an aqueous 4N NaOH solutionwas gradually added dropwise to the suspension, and the obtained mixturewas distilled under reflux for 3 hours. The resultant reaction mixturewas left to stand to room temperature, and then distilled under areduced pressure to remove all volatile materials. Methanol was added tothe concentrate, and the thus-deposited solid was collected byfiltration. The thus-obtained crude product was purified by silica gelchromatography using a hexane/chloroform (5:1-2:1) mixed solvent as aneluent to give 0.39 g of the target2-[3,5-di(9-anthryl)phenyl]-4,6-diphenyl-1,3,5-triazine as white solid(yield: 43%).

¹H-NMR (CDCl₃): δ. 7.49-7.57 (m, 14H), 7.82 (s, 1H), 8.04 (d, J=8.7 Hz,4H), 8.13 (d, J=8.2 Hz, 4H), 8.61 (s, 2H), 8.72 (d, J=8.7 Hz, 4H), 9.08(s, 2H).

The melting point and Tg of the obtained compound are shown in Table 1,below.

Experiment Example 56

In a stream of argon, 1.26 g (5.13 mmol) of 1-pyreneboronic acid, 1.00 g(2.14 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine and60.1 mg (0.081 mmol) of dichlorobis(triphnylphosphine)palladium weresuspended in 75 mL of tetrahydrofuran, and the temperature of theobtained suspension was elevated to 70° C. 4.01 mL (16.1 mmol) of anaqueous 4N NaOH solution was gradually added dropwise to the suspension,and the obtained mixture was distilled under reflux for 3 hours. Theresultant reaction mixture was left to stand to room temperature, andthen distilled under a reduced pressure to remove all volatilematerials. Methanol was added to the concentrate, and the thus-depositedsolid was collected by filtration. The thus-obtained crude product wasrecrystallized from o-xylene to give 1.23 g of the target2-[3,5-di(1-pyrenyl)-phenyl]-4,6-diphenyl-1,3,5-triazine as grayishwhite solid (yield: 81%).

¹H-NMR (CDCl₃): δ. 7.55 (t, J=7.0 Hz, 4H), 7.60 (t, J=7.1 Hz, 2H), 8.08(t, J=7.6, 2H), 8.11-8.21 (m, 7H), 8.24 (d, J=7.5 Hz, 2H), 8.27 (d,J=8.7 Hz, 2H), 8.31 (d, J=8.1 Hz, 2H), 8.38 (d, J=7.8 Hz, 2H), 8.48 (d,J=9.3 Hz, 2H), 8.80 (d, J=7.2 Hz, 4H), 9.20 (s, 2H).

The melting point and Tg of the obtained compound are shown in Table 1,below.

Experiment Example 57

In a stream of argon, 1.29 g (5.81 mmol) of 9-phenanthreneboronic acid,1.20 g (2.42 mmol) of2-(3,5-dibromophenyl)-4,6-di-p-tolyl-1,3,5-triazine and 67.9 mg (0.097mmol) of dichlorobis(triphenylphosphine)palladium were suspended in 108mL of tetrahydrofuran, and the temperature of the obtained suspensionwas elevated to 70° C. 4.53 mL (18.2 mmol) of an aqueous 4N NaOHsolution was gradually added dropwise to the suspension, and theobtained mixture was distilled under reflux for 2 hours. Further, 0.11 g(0.50 mmol) of 9-phenanthreneboronic acid was added, and the obtainedmixture was distilled under reflux for 2 hours. The resultant reactionmixture was left to stand to room temperature, and then distilled undera reduced pressure to remove all volatile materials. Methanol was addedto the concentrate, and the thus-deposited solid was collected byfiltration. The thus-obtained crude product was recrystallized fromo-xylene to give 0.74 g of the target2-[3,5-di(9-phenanthryl)-phenyl]-4,6-di-p-tolyl-1,3,5-triazine asgrayish white solid (yield: 44%).

¹H-NMR (CDCl₃): δ. 2.47 (s, 6H), 7.34 (d, J=8.0 Hz, 4H), 7.65 (t, J=7.6Hz, 2H), 7.69 (t, J=7.4 Hz, 2H), 7.75 (t, J=6.9 Hz, 4H), 7.97 (s, 2H),8.01 (s, 1H), 8.02 (d, J=7.4 Hz, 2H), 8.18 (d, J=8.1 Hz, 2H), 8.66 (d,J=8.2 Hz, 4H), 8.81 (d, J=8.3 Hz, 2H), 8.87 (d, J=8.2 Hz, 2H), 9.07 (s,2H).

The melting point and Tg of the obtained compound are shown in Table 1,below.

Experiment Example 58

In a stream of argon, 1.35 g (4.44 mmol) of9-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)anthracene, 1.00 g (2.02mmol) of 2-(3,5-dibromophenyl)-4,6-di-p-tolyl-1,3,5-triazine and 56.7 mg(0.081 mmol) of dichlorobis-(triphenylphosphine)palladium were suspendedin 100 mL of tetrahydrofuran, and the temperature of the obtainedsuspension was elevated to 70° C. 3.78 mL (15.1 mmol) of an aqueous 4NNaOH solution was gradually added dropwise to the suspension, and theobtained mixture was distilled under reflux for 23.5 hours. Then, 0.20 g(0.66 mmol) of 9-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)anthracene and 14 mg (0.02 mmol) ofdichlorobis(triphenylphosphine)palladium were added, followed bydistillation under reflux for 4 hours. Further, 0.20 g (0.66 mmol) of9-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)anthracene and 14 mg(0.02 mmol) of dichlorobis(triphenylphosphine)palladium were added,followed by distillation under reflux for 1 hour. The resultant reactionmixture was left to stand to room temperature, and then distilled undera reduced pressure to remove all volatile materials. Methanol was addedto the concentrate, and the thus-deposited solid was collected byfiltration. The thus-obtained crude product was recrystallized fromo-xylene to give 0.55 g of the target2-[3,5-di(9-anthryl)phenyl]-4,6-di-p-tolyl-1,3,5-triazine as grayishwhite solid (yield: 39%).

¹H-NMR (CDCl₃): δ. 2.44 (s, 6H), 7.29 (d, J=8.6 Hz, 4H), 7.48-7.56 (m,8H), 7.80 (s, 1H), 8.04 (d, J=8.0 Hz, 4H), 8.13 (d, J=8.0 Hz, 4H), 8.60(d, J=8.2 Hz, 4H), 8.60 (s, 2H), 9.07 (s, 2H).

The melting point and Tg of the obtained compound are shown in Table 1,below.

Experiment Example 59

In a stream of argon, 1.20 g (4.87 mmol) of 1-pyreneboronic acid, 1.50 g(3.03 mmol) of 2-(3,5-dibromophenyl)-4,6-di-p-tolyl-1,3,5-triazine and57 mg (0.081 mmol) of dichlorobis-(triphenylphosphine)palladium weresuspended in 135 mL of tetrahydrofuran, and the temperature of theobtained suspension was elevated to 70° C. 3.81 mL (15.2 mmol) of anaqueous 4N NaOH solution was gradually added dropwise to the suspension,and the obtained mixture was distilled under reflux for 2 hours. Then,29 mg (0.041 mmol) of dichlorobis(triphenylphosphine)palladium wasadded, followed by distillation under reflux for 2 hours. Further, 0.20g (0.81 mmol) of 1-pyreneboronic acid was added, followed bydistillation under reflux for 2 hours. The resultant reaction mixturewas left to stand to room temperature, and then distilled under areduced pressure to remove all volatile materials. Methanol was added tothe concentrate, and the thus-deposited solid was collected byfiltration. The thus-obtained crude product was recrystallized fromo-xylene. The recrystallization by o-xylene was repeated three times intotal to give 1.14 g of the target2-[3,5-di(1-pyrenyl)phenyl]-4,6-di-p-tolyl-1,3,5-triazine as grayishwhite solid (yield: 51%).

¹H-NMR (CDCl₃): δ. 2.46 (s, 6H), 7.33 (d, J=8.0 Hz, 4H), 8.08 (t, J=7.6Hz, 2H), 8.16 (d, J=9.3 Hz, 2H), 8.19 (d, J=3.7 Hz, 4H), 8.21 (s, 1H),8.24 (d, J=7.4 Hz, 2H), 8.27 (d, J=9.0 Hz, 2H), 8.29 (d, J=8.0 Hz, 2H),8.37 (d, J=7.9 Hz, 2H), 8.48 (d, J=9.3 Hz, 2H), 8.67 (d, J=8.2 Hz, 4H),9.18 (s, 2H).

The melting point and Tg of the obtained compound are shown in Table 1,below.

Experiment Example 60

In a stream of argon, 0.52 g (2.36 mmol) of 9-phenanthreneboronic acid,0.91 g (2.15 mmol) of2-(3-bromo-5-chlorophenyl)-4,6-diphenyl-1,3,5-triazine and 24.8 mg(0.022 mmol) of tetrakis(triphenylphosphine) palladium were suspended ina mixed solvent comprised of 80 mL of toluene and 10 mL of ethanol, andthe temperature of the obtained suspension was elevated to 60° C. 6.45mL (6.45 mmol) of an aqueous 1M K₂CO₃ solution was gradually addeddropwise to the suspension, and the obtained mixture was distilled underreflux for 18 hours. The resultant reaction mixture was cooled to roomtemperature, and then distilled under a reduced pressure to remove allvolatile materials. Methanol was added to the concentrate, and thethus-deposited solid was collected by filtration. The thus-obtainedcrude product was dissolved in chloroform and the obtained solution wasfiltered by celite. The filtrate was distilled to remove all volatilematerials to give 1.02 g of an intermediate2-[3-chloro-5-(9-phenanthryl)phenyl]-4,6-diphenyl-1,3,5-triazine asgrayish white solid (yield: 91%).

Then in a stream of argon, 0.5 g (0.96 mmol) of the obtained2-[3-chloro-5-(9-phenanthryl)phenyl]-4,6-diphenyl-, 3,5-triazine, 038 g(1.73 mmol) of 1-naphthaleneboronic acid, 12.9 mg (0.058 mmol) ofpalladium acetate and 1.13 g (3.46 mmol) of cesium carbonate weresuspended in 50 mL of tetrahydrofuran, and the temperature of theobtained suspension was elevated to 70° C. and distilled under refluxfor 40 hours. The resultant reaction mixture was cooled to roomtemperature, and then distilled under a reduced pressure to remove allvolatile materials. Methanol was added to the concentrate, and thethus-deposited solid was collected by filtration. The thus-obtainedcrude product was purified by column chromatography to give 0.56 g ofthe target2-[3-(1-naphthyl)-5-(9-phenanthryl)phenyl]-4,6-diphenyl-1,3,5-triazineas grayish white solid (yield: 95%).

¹H-NMR (CDCl₃): δ. 7.53-7.77 (m, 15H), 7.96 (d, J=9.0 Hz, 2H), 8.00 (t,J=7.7 Hz, 2H), 8.15 (d, J=4.3 Hz, 1H), 8.16 (d, J=4.8 Hz, 1H), 8.78 (d,J=7.0 Hz, 4H), 8.81 (d, 8.5 Hz, 1H), 8.87 (d, J=8.2 Hz, 1H), 9.05 (d,7.7 Hz, 2H).

Experiment Example 61

In a stream of argon, 0.62 g (2.13 mmol) of 9-bromoanthracene, 0.50 g(0.89 mmol) of2-(3,5-bis(4,4,5,5-tetramethyl)-1,3,2-dioxabororan-2-yl)phenyl]-4,6-diphenyl-1,3,5-triazineand 18.7 mg (0.027 mmol) of dichlorobis-(triphenylphosphine)palladiumwere suspended in 40 mL of tetrahydrofuran, and the temperature of theobtained suspension was elevated to 70° C. 1.34 mL (5.34 mmol) of anaqueous 4N NaOH solution was gradually added dropwise to the suspension,and the obtained mixture was distilled under reflux for 3 hours. Theresultant reaction mixture was cooled to room temperature, and thendistilled under a reduced pressure to remove all volatile materials.Methanol was added to the concentrate, and the thus-deposited solid wascollected by filtration. The thus-obtained crude product was purified bysilica gel column chromatography using a hexane/chloroform (5:1-2:1)mixed solvent as an eluent to give 0.32 g of the target2-[3,5-di(9-anthryl)phenyl]-4,6-diphenyl-1,3,5-triazine as white solid(yield: 54%).

¹H-NMR (CDCl₃): δ. 7.49-7.57 (m, 14H), 7.82 (s, 1H), 8.04 (d, J=8.7 Hz,4H), 8.13 (d, J=8.2 Hz, 4H), 8.61 (s, 2H), 8.72 (d, J=8.7 Hz, 4H), 9.08(s, 2H).

Test Example 1

A glass substrate with a transparent indium-tin oxide (ITO) electrodewas prepared, which had a stripe pattern comprised of ITO film with a 2nm width. The substrate was washed with isopropyl alcohol and thensurface-treated by irradiation of ultraviolet rays. Using thesurface-treated substrate, an organic EL device with an emitting area of4 mm² having a multilayer structure as illustrated in FIG. 1 wasmanufactured as follows.

Each layer was formed by vacuum deposition. The glass substrate wasplaced in a vacuum deposition chamber, and the inner pressure wasreduced to 1.0×10⁻⁴ Pa.

As illustrated in FIG. 1, organic compound layers, i.e., a holeinjection layer 2, a hole transport layer 3, an emitting layer 4 and anelectron transport layer 5 were formed in this order on theabove-mentioned glass substrate 1. Further, a cathode layer 6 wasformed.

The hole injection layer 2 was formed by vacuum-depositing phtalocyaninecopper(II), previously purified by sublimation, into a thickness of 25nm. The hole transport layer 3 was formed by vacuum-depositingN,N′-di(naphthylen-1-yl)-N,N′-diphenylbenzidine (NPD) into a thicknessof 45 nm.

The emitting layer 4 was formed by vacuum-depositing a mixture of 97mass % of 4,4′-bis(2,2-diphenylethen-1-yl)diphenyl(DPVBi) and 3 mass %of 4,4′-bis[4-(di-p-tolylamino)phenylethen-1-yl]biphenyl(DPAVBi) into athickness of 40 nm. The electron transport layer 5 was formed byvacuum-depositing2-[4,4″-di(2-pyridyl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-diphenylpyrimidine,synthesized in Experiment Example 1 according to the present invention,into a thickness of 20 nm.

The vacuum deposition of each organic material was conducted bysubjecting each organic material to electric resistance heating to forma thin film at a deposition rate of 0.3 nm/sec to 0.5 nm/sec.

Then, a metal mask was arranged so as to be orthogonal to the ITOstripe, and a cathode layer 6 was vacuum-deposited. The vacuumdeposition of the cathode layer 6 was conducted so as to have a doublelayer structure comprising a lithium fluoride layer with a thickness of0.5 nm and an aluminum layer with a thickness of 100 nm. The measurementof thickness of each organic material thin film layer was conducted bystylus profilometer (“DEKTAK”).

Finally the thus-obtained assembly of multi-layers was encapsulated witha glass cap and ultraviolet ray-curable epoxy resin (available fromNagase Chemtex Corporaton). The encapsulation was conducted in anitrogen atmosphere having an oxygen-and-moisture content of below 1 ppmwithin a glove box.

Luminous properties of the thus-manufactured blue EL device wereevaluated by applying a direct current and using a luminance meter“BM-9” available from Topcon Corporation. The luminous properties, i.e.,voltage (V), luminance (cd/m²), current efficiency (cd/A) and powerefficiency (lm/W) were measured at a current density of 20 mA/cm².

The luminous properties of the manufactured blue fluorescent device wereas follows. Voltage 5.8 V, luminance 2,160 cd/m², current efficiency10.8 cd/A, power efficiency 5.9 lm/W. Luminance half-life of the devicewas 171 hours.

Test Example 2

By the same procedures as described in Test Example 1, an organic ELdevice was manufactured except that an emitting layer 4 was formed byvacuum-depositing tris(8-quinolinolato)aluminum (III) (Alq) into athickness of 40 nm instead of the emitting layer formed fromDPVBi/DPAVBi mixture in Test Example 1.

The thus-manufactured green fluorescent device exhibited a voltage of5.1 V, a luminance of 958 cd/m², a current efficiency of 4.8 cd/A, and apower efficiency of 2.9 lm/W. Luminance half-life of the device was1,618 hours.

Test Example 3

By the same procedures as described in Test Example 1, an organic ELdevice was manufactured except the hole injection layer 2, the holetransport layer 3, the emitting layer 4 and the electron transport layer5 were formed as follows.

The hole injection layer 2 was formed by vacuum-depositing phtalocyaninecopper(II), previously purified by sublimation, into a thickness of 10nm. The hole transport layer 3 was formed by vacuum-depositingN,N′-di(naphthylen-1-yl)-N,N′-diphenylbenzidine (NPD) into a thicknessof 30 nm. The emitting layer 4 was formed by co-vacuum-depositing into athickness of 30 nm a host material of 4,4′-di(carbazol-9-yl)biphenyl(CBP) and a dopant of tris(2-phenylpyridine)iridium (III) (Ir(ppy)₃) ata dope concentration of 6%.

The electron transport layer 5 was formed by vacuum-depositing2-[4,4″-di(2-pyridyl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-diphenylpyrimidine,synthesized in Experiment Example 1 according to the present invention,into a thickness of 50 nm. All other conditions and procedures remainedthe same.

The thus-manufactured green phosphorescent device exhibited a voltage of7.5 V, a luminance of 6,610 cd/m², a current efficiency of 33.5 cd/A,and a power efficiency of 13.9 lm/W. Luminance half-life of the devicewas 230 hours.

Test Example 4

By the same procedures as described in Test Example 1, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing2-[3,3″-di(2-pyridyl)-1,1′:3′,1″-terphenyl-5′-yl]-4,6-diphenylpyrimidineinto a thickness of 20 nm instead of the electron transport layer formedin Test Example 1.

The thus-manufactured blue fluorescent device exhibited a voltage of 6.3V, a luminance of 2,110 cd/m², a current efficiency of 10.6 cd/A, and apower efficiency of 5.3 lm/W. Luminance half-life of the device was 165hours.

Comparative Test Example 1

By the same procedures as described in Test Example 1, an organic ELdevice was manufactured except that an electron transport layer 5 wasformed by vacuum-depositing Alq into a thickness of 20 nm instead of theelectron transport layer 5 formed from the cyclic azine derivative ofthe present invention.

The thus-manufactured blue fluorescent device exhibited a voltage of 7.1V, a luminance of 1,883 cd/m², a current efficiency of 9.4 cd/A, and apower efficiency of 4.2 lm/W. Luminance half-life of the device was 163hours.

Comparative Test Example 2

By the same procedures as described in Test Example 2, an organic ELdevice was manufactured except that an electron transport layer 5 wasformed by vacuum-depositing Alq into a thickness of 20 nm instead of theelectron transport layer 5 formed from the cyclic azine derivative ofthe present invention.

The thus-manufactured green fluorescent device exhibited a voltage of5.6 V, a luminance of 957 cd/m², a current efficiency of 4.8 cd/A, and apower efficiency of 2.6 lm/W. Luminance half-life of the device was1,318 hours.

Comparative Test Example 3

By the same procedures as described in Test Example 3, an organic ELdevice was manufactured except that an electron transport layer 5 wasformed by vacuum-depositing Alq into a thickness of 50 nm instead of theelectron transport layer 5 formed from the cyclic azine derivative ofthe present invention.

The thus-manufactured green phosphorescent device exhibited a voltage of7.7 V, a luminance of 3,850 cd/m², a current efficiency of 16.9 cd/A,and a power efficiency of 6.7 lm/W. Luminance half-life of the devicewas 271 hours.

Comparative Test Example 4

By the same procedures as described in Test Example 3, an organic ELdevice was manufactured except that an electron transport layer 5 wasformed by vacuum-depositing BAlq(bis(2-methyl-8-quinolinolato)-4-phenylphenolat-aluminum) into athickness of 5 nm and Alq into a thickness of 45 nm in this orderinstead of the electron transport layer 5 formed from the cyclic azinederivative of the present invention.

The thus-manufactured green phosphorescent device exhibited a voltage of9.3 V, a luminance of 6,170 cd/m², a current efficiency of 30.9 cd/A,and a power efficiency of 10.4 lm/W. Luminance half-life of the devicewas 202 hours.

Test Example 5

By the same procedures as described in Test Example 1, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing2-[5-(9-phenanthryl)-4′-(2-pyridyl)biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazine,synthesized in Experiment Example 15 according to the present invention,into a thickness of 20 nm instead of the electron transport layer formedin Test Example 1.

The thus-manufactured blue fluorescent device exhibited a voltage of 5.3V, and a current efficiency of 10.5 cd/A. Luminance half-life of thedevice was 155 hours.

Test Example 6

By the same procedures as described in Test Example 5, an organic ELdevice was manufactured except the emitting layer 4 was formed byvacuum-depositing Alq₃ into a thickness of 40 nm instead of the emittinglayer 4 in Test Example 5.

The thus-manufactured EL device exhibited a voltage of 5.2 V and acurrent efficiency of 2.5 cd/A at a current density of 20 mA/cm².Luminance half-life of the device was 2015 hours.

Test Example 7

By the same procedures as described in Test Example 5, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing Alq₃ into a thickness of 20 nm instead of theelectron transport layer 5 in Test Example 5.

The thus-manufactured EL device exhibited a voltage of 6.9 V and acurrent efficiency of 6.1 cd/A at a current density of 20 mA/cm².Luminance half-life of the device was 53 hours.

Test Example 8

By the same procedures as described in Test Example 6, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing Alq₃ into a thickness of 20 nm instead of theelectron transport layer 5 in Test Example 6.

The thus-manufactured EL device exhibited a voltage of 5.4 V and acurrent efficiency of 4.3 cd/A at a current density of 20 mA/cm².

Luminance half-life of the device was 1,785 hours.

Test Example 9

By the same procedures as described in Test Example 5, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing4,6-diphenyl-2-[5-(1-naphthyl)-4′-(2-pyridyl)biphenyl-3-yl]-1,3,5-triazineinto a thickness of 20 nm instead of the electron transport layer 5 inTest Example 5.

The thus-manufactured EL device exhibited a voltage of 6.0 V and acurrent efficiency of 11.1 cd/A at a current density of 20 mA/cm².

Luminance half-life of the device was 113 hours.

Test Example 10

By the same procedures as described in Test Example 5, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing2-[5-(9-phenanthryl)-3′-(3-pyridyl)biphenyl-3-yl]-1,3,5-triazine into athickness of 20 nm instead of the electron transport layer 5 in TestExample 5.

The thus-manufactured EL device exhibited a voltage of 6.1 V and acurrent efficiency of 11.5 cd/A at a current density of 20 mA/cm².Luminance half-life of the device was 117 hours.

Test Example 11

By the same procedures as described in Test Example 5, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing2-[3-(2,2′-bipyridin-6-yl)-5-(9-phenanthryl)phenyl]-4,6-diphenyl-1,3,5-triazineinto a thickness of 20 nm instead of the electron transport layer 5 inTest Example 5.

The thus-manufactured EL device exhibited a voltage of 5.3 V and acurrent efficiency of 8.0 cd/A at a current density of 20 mA/cm².

Test Example 12

By the same procedures as described in Test Example 5, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing4,6-diphenyl-2-[5-(9-phenanthryl)-3′-(2-pyridyl)biphenyl-3-yl]-1,3,5-triazineinto a thickness of 20 nm instead of the electron transport layer 5 inTest Example 5.

The thus-manufactured EL device exhibited a voltage of 6.6 V and acurrent efficiency of 9.7 cd/A at a current density of 20 mA/cm².

Test Example 13

By the same procedures as described in Test Example 5, an organic ELdevice was manufactured except the hole injection layer 2, the holetransport layer 3, the emitting layer 4 and the electron transport layer5 were formed as follows.

The hole injection layer 2 was formed by vacuum-depositing phtalocyaninecopper(II) into a thickness of 10 nm. The hole transport layer 3 wasformed by vacuum-depositingN,N′-bis(1-naphthyl)-N,N′-diphenyl-4,4′-biphenyl (NPD) into a thicknessof 30 nm. The emitting layer 4 was formed by vacuum-depositing into athickness of 30 nm a mixture of 4,4′-bis(9H-carbazol-9-yl)biphenyl (CBP)and tris(2-phenylpyridinato)iridium (III) (Ir(ppy)₃) at a ratio of 94:6by weight.

The electron transport layer 5 was formed by vacuum-depositingbis(2-methyl-8-quinolinolato)-4-phenylphenolato-aluminum (BAlq) into athickness of 5 nm and2-[5-(9,9-dimethylfluoren-2-yl)-4′-(2-pyridyl)biphenyl-3-yl]-4,6-diphenyl-,3,5-triazine into a thickness of 45 nm in this order. All otherconditions and procedures remained the same as in Test Example 5.

The thus-manufactured EL device exhibited a voltage of 7.7 V and acurrent efficiency of 29.2 cd/A at a current density of 20 mA/cm².

Test Example 14

By the same procedures as described in Test Example 13, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositingbis(2-methyl-8-quinolinolato)-4-phenylphenolato-aluminum (BAlq) into athickness of 5 nm and then vacuum-depositing Alq₃ into a thickness of 45nm instead of the electron transport layer 5 in Test Example 13.

The thus-manufactured EL device exhibited a voltage of 9.0 V and acurrent efficiency of 26.7 cd/A at a current density of 20 mA/cm².

Test Example 15

By the same procedures as described in Test Example 1, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing 2-[3,5-bis(2,2′:6′,2″-terpyridin-4′-yl)phenyl]-4,6-diphenyl-1,3,5-triazine, synthesizedin Experiment Example 44, into a thickness of 20 nm instead of theelectron transport layer 5 in Test Example 1.

The thus-manufactured EL device exhibited a voltage of 5.5 V, aluminance of 2,230 cd/m², a current efficiency of 11.2 cd/A and a powerefficiency of 6.4 lm/W. Luminance half-life of the device was 113 hours.

Test Example 16

By the same procedures as described in Test Example 15, an organic ELdevice having a multilayer structure as illustrated in FIG. 1 wasmanufactured by forming the hole injection layer 2, the hole transportlayer 3, the emitting layer 4, the electron transport layer 5 and acathode layer 6 in this order on the glass substrate 1, wherein the holeinjection layer 2, the hole transport layer 3, the emitting layer 4 andthe electron transport layer 5 were formed as follows. All otherconditions and procedures remained the same.

The hole injection layer 2 was formed by vacuum-depositing phtalocyaninecopper(II), previously purified by sublimation, into a thickness of 10nm. The hole transport layer 3 was formed by vacuum-depositingN,N′-di(1-naphthyl)-N,N′-diphenylbenzidine (NPD) into a thickness of 30nm.

The emitting layer 4 was formed by vacuum-depositing into a thickness of30 nm a mixture of 4,4′-bis(9-carbazolyl)biphenyl (CBP) andtris(2-phenylpyridine)iridium (III) (Ir(ppy)₃) at a ratio of 94:6 byweight. The electron transport layer 5 was formed by vacuum-depositing2-[3,5-bis(2,2′:6′,2″-terpyridin-4′-yl)phenyl]-4,6-diphenyl-1,3,5-triazine,synthesized in Experiment Example 44 according to the present invention,into a thickness of 50 nm.

The thus-manufactured EL device exhibited a voltage of 8.4 V, aluminance of 4,030 cd/m², a current efficiency of 20.2 cd/A, and a powerefficiency of 7.5 lm/W. Luminance half-life of the device was 82 hours.

Test Example 17

By the same procedures as described in Test Example 15, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing a conventional electron transport material, Alq,into a thickness of 20 nm instead of the electron transport layer 5 inTest Example 15.

The thus-manufactured EL device exhibited a voltage of 7.2 V, aluminance of 1,859 cd/m², a current efficiency of 9.3 cd/A and a powerefficiency of 4.0 lm/W. Luminance half-life of the device was 83 hours.

Test Example 18

By the same procedures as described in Test Example 16, an organic ELdevice was manufactured except the electron transport layer 5 was formedby vacuum-depositing a conventional electron transport material, Alq,into a thickness of 50 nm instead of the electron transport layer 5 witha thickness of 20 nm in Test Example 16.

The thus-manufactured EL device exhibited a voltage of 10.4 V, aluminance of 3,450 cd/m², a current efficiency of 17.3 cd/A and a powerefficiency of 5.2 lm/W. Luminance half-life of the device was 108 hours.

Test Example 19

In this example, a mobility measuring element was manufactured andevaluated.

A glass substrate having an indium-tin oxide (ITO) transparent electrodewas prepared, which had a stripe pattern comprised of ITO films with a 2mm width. The glass substrate was washed with isopropyl alcohol and thensurface-treated by irradiation of ultraviolet rays. Amobility-determining organic material was vacuum-deposited on thesurface-treated substrate as described in detail below.

The glass substrate was placed in a vacuum deposition chamber, and itsinner pressure was reduced to 3.6×10⁻⁶ Torr, and2-[3,5-di(1-pyrenyl)phenyl]-4,6-diphenyl-1,3,5-triazine wasvacuum-deposited on the substrate at a deposition rate of 3 to 5angstrom/sec by electrical resistance heating. The thus-formed thin filmhad a thickness of 1.8 μm as measured by stylus profilometer (DEKTAK).

A metal mask was arranged so as to be orthogonal to the ITO stripe, andan aluminum thin film with a width of 2 mm and a thickness of 100 nm wasformed by vacuum deposition. Thus, a working area with 2 mm square formeasuring mobility was formed. The substrate having the working area wasencapsulated with ultraviolet ray-curable epoxy resin (available fromNagase Chemtex Corporation). The encapsulation was conducted in anitrogen atmosphere having an oxygen-and-moisture content of below 1 ppmwithin a glove box.

The measurement of mobility using the above-mentioned mobility measuringelement will be described.

The mobility of charge transport material can be measured by variousmethods, but, a generally adopted time-of-flight mobility measuringmethod was used. The measurement of mobility was made by determining therate of transfer to the Al electrode, of charge generated uponirradiation of nitrogen laser from the transparent ITO electrode side.The measurement was made at room temperature using a mobility measuringapparatus available from Optel Co., Ltd., Japan.

The mobility of 2-[3,5-di(1-pyrenyl)phenyl]-4,6-diphenyl-1,3,5-triazinewas 7.6×10⁻⁵ cm²/V·sec. This mobility value was higher than that (1×10⁻⁶cm²/V·sec) of hydroxyquinolinealuminum complex (Alq) which is theconventional electron transport material described in JP 2002-158091 A.

Test Example 20

By the same method as mentioned in Test Example 19, mobility of2-[3,5-di(9-phenanthryl)phenyl]-4,6-di-p-tolyl-1,3,5-triazine wasmeasured. The mobility was 2.4×10⁻⁵ cm²/V·sec.

Test Example 21

By the same method as mentioned in Test Example 19, mobility of2-[3,5-di(1-pyrenyl)phenyl]-4,6-di-p-tolyl-1,3,5-triazine was measured.The mobility was 6.0×10⁻⁵ cm²/V·sec.

Test Example 22

By the same method as mentioned in Test Example 19, mobility of2-[3,5-di(9-anthryl)phenyl]-4,6-diphenyl-1,3,5-triazine was measured.The mobility was 2.9×10⁻⁴ cm²/V·sec.

Test Example 23

Measurement of melting point and Tg of cyclic azine derivativesaccording to the present invention showed that the melting point and Tgwere higher than those of an azine derivative A, represented by thefollowing formula, and described in JP 2008-280330 A. The melting pointand Tg of cyclic azine derivatives according to the present inventionand the azine derivative A are shown in Table 1, below.

TABLE 1 Melting point (° C.) Tg (° C.) Example 54 357 147 Example 55 407142 Example 56 340 155 Example 57 325 156 Example 58 388 — Example 59340 160 Azine derivative A 279 108

As seen from the above-mentioned working examples, it was confirmed thatthe cyclic azine derivatives according to the present invention givefluorescent or phosphorescent EL devices which are drivable at a lowpower consumption and exhibit a prolonged life. The cyclic azinederivative of the present invention suitable not only as a material forthe emitting layer in an organic EL devices as specifically described inthe above Test Examples, but also as a material for other fluorescent orphosphorescent EL devices and for coated EL devices.

The organic EL devices of the present invention can be applied broadlyto fields including flat panel displays, and lighting equipments towhich low power consumption and long life are required.

INDUSTRIAL APPLICABILITY

The cyclic azine compound having the novel chemical structure accordingto the present invention is suitable as an organic compound layer offluorescent or phosphorescent EL devices. Especially when the cyclicazine compound is used for an electron transport layer, the fluorescentor phosphorescent EL devices exhibit improved derivability at a lowpower consumption and enhanced light emission at high efficiency.

More specifically, thin films of the cyclic azine compound according tothe present invention has outstanding properties in surface smoothness,amorphousness, heat resistance, electron transportability, hole blockingcapability, resistance to oxidation and reduction, moisture resistance,oxygen resistance and electron injection property. Therefore, said filmis useful as a material for an organic EL device, especially as amaterial for an electron transport layer, a hole blocking layer and alight emitting host layer of an organic EL device. The cyclic azinecompound according to the present invention is also a wide band-gapcompound, therefore, it is suitable for not only fluorescent EL devicesbut also phosphorescent EL devices.

What is claimed is:
 1. A cyclic azine compound represented by theformula (1):

wherein, in the formula (1), each Ar¹ represents phenyl group, p-tolylgroup, m-tolyl group, o-tolyl group, 2,6-dimethylphenyl group,4-tert-butylphenyl group, 4-biphenylyl group, 3-biphenylyl group,2-biphenylyl group, 3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenylgroup, 3-(4-pyridyl)phenyl group, or 4-(4-pyridyl)phenyl group; and Arepresents a group selected from the group consisting of those which arerepresented by the following formulae (2) to (4):

wherein, in the formula (2), each Ar² represents a substituted phenylgroup or a condensed aromatic hydrocarbon group not having a 16 groupelement, provided that a 1,3,5-trimethylphenyl group is excluded fromAr²;

wherein, in the formula (3), Ar³ represents a phenyl group, a pyridylgroup or a pyrimidyl group; Ar⁴ represents an anthryl group which isunsubstituted or substituted by an alkyl group having 1 to 4 carbonatoms or a phenyl group, a phenanthryl group which is unsubstituted orsubstituted by an alkyl group having 1 to 4 carbon atoms or a phenylgroup, a fluorenyl group which is unsubstituted or substituted by analkyl group having 1 to 4 carbon atoms or a phenyl group, abenzofluorenyl group which is unsubstituted or substituted by an alkylgroup having 1 to 4 carbon atoms or a phenyl group, an unsubstitutedpyrenyl group, an unsubstituted triphenylenyl group; X represents aphenylene group or a pyridylene group; p represents an integer of 0 to 2provided that, when p is 2, the two Xs may be the same or different; andZ¹ represents a carbon atom;

wherein, in the formula (4), each Ar⁵ represents a pyridyl group, andeach Ar⁶ represent a phenyl group or a pyridyl group; Z² represents acarbon atom and each Z³ represents a carbon atom or a nitrogen atom. 2.The cyclic azine compound according to claim 1, wherein each Ar² in theformula (2) represents a phenyl group substituted by an alkyl grouphaving 1 to 4 carbon atoms, a phenyl group substituted by a halogenatom, a phenyl group substituted by an unsubstituted or substitutedphenyl group, a phenyl group substituted by an unsubstituted orsubstituted pyrimidinyl group, a phenyl group substituted by anunsubstituted or substituted thiazolyl group, a phenyl group substitutedby a pyridyl group, or a phenyl group substituted by a phenanthrolinylgroup.
 3. The cyclic azine compound according to claim 1, wherein eachAr² in the formula (2) represents a quinolyl group.
 4. The cyclic azinecompound according to claim 1, wherein Ar⁴ in the formula (3) representsan anthryl group which is unsubstituted or substituted by a phenylgroup, a phenanthryl group which is unsubstituted or substituted by aphenyl group, a fluorenyl group which is unsubstituted or substituted bya phenyl group, a benzofluorenyl group which is unsubstituted orsubstituted by a phenyl group, an unsubstituted pyrenyl group, or anunsubstituted triphenylenyl group.
 5. The cyclic azine compoundaccording to claim 1, wherein Ar⁴ in the formula (3) represents anunsubstituted anthryl group, a unsubstituted phenanthryl group, aunsubstituted fluorenyl group, a unsubstituted benzofluorenyl group, anunsubstituted pyrenyl group, or an unsubstituted triphenylenyl group. 6.The cyclic azine compound according to claim 1, wherein Ar³ in theformula (3) represents a phenyl group or a pyridyl group.
 7. A processfor preparing a cyclic azine compound represented by the formula (1a):

wherein, in the formula (1a), each Ar¹ represents phenyl group, p-tolylgroup, m-tolyl group, o-tolyl group, 2,6-dimethylphenyl group,4-tert-butylphenyl group, 4-biphenylyl group, 3-biphenylyl group,2-biphenylyl group, 3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenylgroup, 3-(4-pyridyl)phenyl group, or 4-(4-pyridyl)phenyl group, and eachAr² represents a substituted phenyl group or a condensed aromatichydrocarbon group not having a 16 group element, provided that a1,3,5-trimethylphenyl group is excluded from Ar²; characterized bycoupling a compound represented by the formula (6) with a compoundrepresented by the formula (7) in the presence of a palladium catalystand in the presence or absence of a base;

wherein, in the formula (6), each Ar¹ is the same as defined above; andeach Y¹ represents a chlorine, bromine or iodine atom;Ar²-M  (7) wherein, in the formula (7), Ar² is the same as definedabove; and M represents a metal group or a hetero atom group.
 8. Aprocess for preparing a cyclic azine compound represented by the formula(1a):

wherein, in the formula (1a), each Ar¹ represents phenyl group, p-tolylgroup, m-tolyl group, o-tolyl group, 2,6-dimethylphenyl group,4-tert-butylphenyl group, 4-biphenylyl group, 3-biphenylyl group,2-biphenylyl group, 3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenylgroup, 3-(4-pyridyl)phenyl group, or 4-(4-pyridyl)phenyl group, and eachAr² represents a substituted phenyl group or a condensed aromatichydrocarbon group not having a 16 group element, provided that a1,3,5-trimethylphenyl group is excluded from Ar²; characterized bycoupling a compound represented by the formula (8) with a compoundrepresented by the formula (9) in the presence of a palladium catalystand a base;

wherein, in the formula (8), each Ar¹ is the same as defined above; eachR¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atomsor a phenyl group; and groups R¹ in the two —B(OR¹) groups may be thesame or different, and two groups R¹ in each of the two —B(OR¹) groupsmay form a ring together with the oxygen atoms and the boron atom;Ar²—Y¹  (9) wherein, in the formula (9), Ar² is the same as definedabove; and Y¹ represents a chlorine, bromine or iodine atom.
 9. Theprocess for preparing a cyclic azine compound according to claim 7,wherein the palladium catalyst has a tertiary phosphine as a ligand. 10.The process for preparing a cyclic azine compound according to claim 7,wherein the metal group or the hetero atom group, represented by M inthe formulae (7) and (11), is a group represented by the followingformula:—B(OR¹)₂ or —ZnR₂ wherein R¹ represents a hydrogen atom, an alkyl grouphaving 1 to 4 carbon atoms or a phenyl group; two groups R¹ in the group—B(OR¹)₂ may be the same or different and the two groups R¹ in the group—B(OR¹)₂ may form a ring together with the oxygen atoms and the boronatom; and R² represents a halogen atom.
 11. An organicelectroluminescent device comprising as a constituent a cyclic azinecompound represented by the formula (1):

wherein, in the formula (1), each Ar¹ is the same as defined in claim 1;and A represents a group selected from the group consisting of thosewhich are represented by the following formulae (2) to (4):

wherein, in the formula (2), each Ar² is the same as defined in claim 1;

wherein, in the formula (3), Ar³ is the same as defined in claim 1; Xrepresents a phenylene group or a pyridylene group; p represents aninteger of 0 to 2 provided that, when p is 2, the two Xs may be the sameor different; and Z¹ represents a carbon;

wherein, in the formula (4), each Ar⁵ is the same as defined in claim 1,and each Ar⁶ is the same as defined in claim 1; Z² represents a carbonatoms, and each Z³ represent a carbon atom or a nitrogen atom.
 12. Theprocess for preparing a cyclic azine compound according to claim 8,wherein the palladium catalyst has a tertiary phosphine as a ligand. 13.The cyclic azine compound according to claim 1, wherein each X in theformula (3) represents a para- or meta-phenylene group or a para- ormeta-pyridylene group; p represents an integer of 0 to 2 provided that,when p is 2, the two Xs may be the same or different.
 14. The cyclicazine compound according to claim 1, wherein each X in the formula (3)represents a para- or meta-phenylene group or a para- or meta-pyridylenegroup; p represents an integer of 0 or 1.